The Predictive Power of the Annellation Theory: The Case of the

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The Predictive Power of the Annellation Theory: The Case of the C H Cata-Condensed Benzenoid Polycyclic Aromatic Hydrocarbons 26

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Jorge O Oña-Ruales, and Yosadara Ruiz-Morales J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.5b07681 • Publication Date (Web): 30 Sep 2015 Downloaded from http://pubs.acs.org on September 30, 2015

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The Journal of Physical Chemistry

The Predictive Power of the Annellation Theory: The Case of the C26H16 Cata-Condensed Benzenoid Polycyclic Aromatic Hydrocarbons

Jorge O. Oña-Ruales1* and Yosadara Ruiz-Morales2

1

National Institute of Standards and Technology, NIST, Gaithersburg, Maryland 20899

2

Instituto Mexicano del Petróleo, Eje Central Lázaro Cárdenas Norte 152, Mexico City 07730,

Mexico

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ABSTRACT The Annellation Theory was applied to establish the locations of maximum absorbance for the p and β bands in the UV-Vis spectra of eight benzenoid cata-condensed polycyclic aromatic hydrocarbons, PAHs, with molecular formula C26H16 and no available syntheses procedures. In this group of eight isomers, there are seven compounds with potential carcinogenic properties due to geometrical constraints. In addition, crude oil and asphaltene absorption spectra exhibit similar properties, and the PAHs in heavier crude oils and asphaltenes are known to be the source of the color of heavy oils. Therefore, understanding the electronic bands of PAHs is becoming increasingly important. The methodology was validated using information for the remaining 29 isomers with available UV-Vis spectra. The results satisfactorily agree with the results from semi-empirical calculations made using the ZINDO/S approach. The locations of maximum absorbance for the p and β bands in the UV-Vis spectra of the eight C26H16 catacondensed isomers dibenzo[c,m]tetraphene, naphtho[1,2-c]chrysene, dibenzo[c,f]tetraphene, benzo[f]picene, naphtho[2,1-a]tetraphene, naphtho[2,1-c]tetraphene, dibenzo[c,l]chrysene, and naphtho[1,2-a]tetraphene were established for the first time. KEYWORDS Polycyclic Aromatic Hydrocarbons, Ultraviolet-Visible Spectrum, Annellation Theory, ZINDO/S Calculations, C26H16 compounds


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1. INTRODUCTION The benzenoid polycyclic aromatic hydrocarbons, PAHs, with cata-condensed configuration (also known as ortho-fused PAHs in IUPAC nomenclature), C(10+4x)H(8+2x) (where x=1… ∞), are linear, angular, and/or multi-branched molecules formed by aromatic carbon atoms situated in one or a maximum of two molecular constitutive rings. The C26H16 group composed of 37 members, as it is presented in Figure 1,1 is among the most important groups in the catacondensed class due to its combination of relatively low molecular mass structures (328 Daltons), low number of isomers (37), and an elevated percent (57%) of structures with steric hindrance regions, e.g., cove, fjord, and helical regions. Specifically, out of the 37 C26H16 catacondensed PAHs, 21 structures (Groups 3, 4, and 5 in Figure 1) are geometrically constrained, i.e., nonplanar. The 21 nonplanar structures are distributed in the following arrangement: 16 structures (Group 3) contain 1 or 2 cove regions and 0, 1, or 2 bay regions; 4 structures (Group 4) contain 1 fjord region and 0, 1, or 2 bay regions; and 1 structure (Group 5) contains one helical region. Comprehensive analyses have been performed about the influence of the geometric constraints on the biological activity of PAHs, e.g., carcinogenic potential, and conclusive relationships that demonstrate the connection of the nonplanar geometry with the carcinogenicity have been achieved.4,5 For example, compound XVII, presents a carcinogenic behavior that has been associated with its constrained geometry.5 Thus, the link between nonplanarity of PAHs and their evidenced biological behavior suggests that not only compound XVII but also the other 20 constrained C26H16 PAHs may possibly constitute compounds with potential harmful biological activity. In spite of this fact, only 13 structures (XVII, XVIII, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXXIII, XXXIV, XXXV, and XXXVII) in the group of 21 C26H16 cata-condensed PAHs with geometrical constraint have reported synthesis 3 ACS Paragon Plus Environment


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procedures (Reference 2 reports the syntheses of XVIII, XX, and XXXVII; Reference 5 reports the synthesis of XVII; Reference 6 reports the syntheses of XXI and XXV; Reference 7 reports the synthesis of XXII; Reference 8 reports the syntheses of XXIII and XXXIII; Reference 9 reports the syntheses of XXIV, XXVI, and XXXIV; and Reference 10 reports the synthesis of XXXV) and 1 structure (XIX) has an unreported synthesis procedure from W. Schmidt. Consequently, there are still seven (XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, and XXXVI) compounds with potential detrimental properties that have not yet been synthesized. Hence, the need exists for establishing experimental or theoretical procedures that lead to the characterization of these seven nonplanar C26H16 cata-condensed PAHs with prospective unfavorable behavior. The UV-Vis spectrum is a fingerprint that characterizes each PAH molecule. As illustrated in Figure 2, the UV-Vis spectrum of pyrene (XXXVIII) shows three types of spectral bands:11 First, the β bands located at lower wavelengths indicate a transition from the highest occupied molecular orbital (HOMO) to the second lowest unoccupied orbital; second, the p bands located at intermediate wavelengths indicate a transition from the HOMO to the lowest unoccupied molecular orbital (LUMO); and third, the α bands generally located at high wavelengths indicate a transition from the second highest occupied molecular orbital to the LUMO. Based on this classification, the UV-Vis spectra of cata-condensed PAHs are characterized by the following unique features that differentiate them from the UV-Vis spectra of peri-condensed PAHs:2 1. The absorbance intensity average ratio of the β bands versus the p bands (approx. 6) is three times larger than that of the analogous absorbance intensity average ratio of peri-condensed PAHs (approx. 2); and


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2. The presence of UV-Vis spectral patterns with bundles of absorption bands that are not welldefined as illustrated in Figure 3 for PAHs XXXIX, XVII, and XL, in opposition to the UV-Vis spectral patterns with regularly distributed and distinct absorption bands for peri-condensed PAHs, as illustrated in Figure 3 for PAHs XXXVIII, XLI, and XLII. Thus, it is apparent that magnitude and shape of the UV-Vis spectral bands are key factors that differentiate the UV-Vis spectra of the cata-condensed PAHs from the UV-Vis spectra of the peri-condensed PAHs. In addition, the locations of maximum absorbance of the bands in the UVVis spectra provide insightful information about the identity of a PAH molecule. However, a relationship that leads to a successful comparison between the average values of the location of maximum absorbance for cata-condensed behavior and the corresponding average values for peri-condensed behavior cannot be established due to the large variability in values reported for each PAH class. For cata-condensed PAHs, the location of maximum absorbance of the longest β band covers a range from 221 to 391 nm and the location of maximum absorbance of the longest p band covers a range from 284 to 582 nm.2 On the other hand, for peri-condensed PAHs, the location of maximum absorbance of the longest β band covers a range from 251 to 486 nm and the location of maximum absorbance of the longest p band covers a range from 328 to 738 nm.2 Due to this challenging scenario, the annellation, i.e., the addition (or subtraction) of rings to certain positions of the rings that form a molecule, e.g., PAH, and the direct application of this concept in the methodology named the annellation theory2 will be used for the calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the seven C26H16 cata-condensed PAHs, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, and XXXVI, with no reference standards available and with prospective biological activity. The predictive power of the annellation theory was already presented, discussed, validated, and applied in a 5 ACS Paragon Plus Environment


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preceding article12 for the calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the peri-condensed PAHs C32H16. As an extra assignment for the method, the calculation of the locations of maximum absorbance of the p and β bands in the UVVis spectrum of the remaining C26H16 cata-condensed PAH, XVI, with no reference standard available, with only bay structural regions, and thus, with no anticipated carcinogenic potential, will also be performed. It is expected that the results achieved through the annellation theory methodology will provide reliable information about the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the eight C26H16 cata-condensed PAHs under consideration. It is the first time that the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of dibenzo[c,m]tetraphene, XVI; naphtho[1,2-c]chrysene, XXVII; dibenzo[c,f]tetraphene, XXVIII; benzo[f]picene, XXIX; naphtho[2,1-a]tetraphene, XXX; naphtho[2,1-c]tetraphene, XXXI; dibenzo[c,l]chrysene, XXXII; and naphtho[1,2-a]tetraphene, XXXVI, are reported. 2. THEORETICAL METHODS 2.1. Overall Procedure Analogous to the procedure for calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the C32H16 peri-condensed PAHs,12 the procedure for calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the C26H16 cata-condensed PAHs is composed of validation, elucidation, and substantiation. Validation involves the comparison of the locations of maximum absorbance of the p and β bands calculated using the annellation theory technique shown in Figure 412 and the locations of maximum absorbance of the p and β bands available for the already synthesized 29 C26H16 cata6 ACS Paragon Plus Environment

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condensed PAHs (Reference 2 reports the UV-Vis spectra of II, IV, V, VI, VII, VIII, IX, X, XI, XII, XIV, XVIII, XX, and XXXVII; Reference 5 reports the UV-Vis spectrum of XVII; Reference 6 reports the UV-Vis spectra of XXI and XXV; Reference 7 reports the UV-Vis spectrum of XXII; Reference 8 reports the UV-Vis spectra of XXIII and XXXIII; Reference 9 reports the UV-Vis spectra of XXIV, XXVI, and XXXIV; Reference 10 reports the UV-Vis spectrum of XXXV; Reference 13 reports the UV-Vis spectrum of I; Reference 14 reports the UV-Vis spectrum of III; Reference 15 reports the UV-Vis spectrum of XIII; Reference 16 reports UV-Vis spectrum of XV; and the UV-Vis spectrum of XIX comes from unreported results by W. Schmidt). Next, elucidation involves the calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the eight C26H16 cata-condensed PAHs with no available syntheses procedures using the annellation theory method shown in Figure 4. Finally, substantiation comprises the comparison among the reference standards available, the annellation theory calculations, and the ZINDO/S methodology for the locations of the p1 and β1 bands in the UV-Vis spectra of the 37 C26H16 cata-condensed PAHs. 2.2. Mathematical Technique The mathematical technique based on the annellation theory illustrated in Figure 4 for the calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectrum of PAH 4, using as references PAHs 1, 2, and 3, has the following steps:12 1. Determination of the structures of the reference PAHs 1, 2, and 3 that satisfy the restrictions of structural and aromatic relationship between PAHs 1 and 2, and PAHs 3 and 4, and the restriction of structural and aromatic enclosure between PAHs 1 and 3. The structural 7 ACS Paragon Plus Environment


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relationship, given by the shape of the molecules, and the aromatic relationship, given by the positions of the sextets and double bonds, between PAHs 1 and 2 should be equivalent to the respective structural-aromatic relationship between PAHs 3 and 4. Also, PAH 1 should be structurally and aromatically enclosed in PAH 3 so as to connect the top and the bottom part of the scheme. 2. Calculation of the difference between the locations of maximum absorbance of the p bands and the difference between the locations of maximum absorbance of the β bands of the reference PAHs 1 and 2. 3. Addition of the calculated differences (from Step 2) to the locations of maximum absorbance of the p bands and to the locations of maximum absorbance of the β bands of the reference PAH 3 to find the locations of maximum absorbance of the p and β bands in the UVVis spectrum of PAH 4. 2.3. ZINDO/S Semi-Empirical Calculations ZINDO/S semi-empirical calculations were made to determine the locations of maximum absorbance of the p and β bands for the 37 C26H16 cata-condensed PAHs. Geometry optimization of the PAH systems was first carried out by performing force field-based minimization using the energy minimization panel in the Cerius 2 program17 and the COMPASS (Condensed-Phase Optimized Molecular Potentials for Atomistic Simulation Studies)18,19 consistent force field structures as they are provided in the Cerius 2 package. The excited electronic states for the PAH systems were then calculated using the ZINDO/S20 approach, which is a semi-empirical electronic structure method calibrated for calculating excited states, as implemented in the Cerius 2 program, using the COMPASS force field geometry optimized structures. This method has 8 ACS Paragon Plus Environment

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provided satisfactory agreement with experimental values for the calculation of optical properties of PAHs. We have previously demonstrated12,21 that values calculated for the electronic transitions of PAHs using the ZINDO/S methodology present deviations of 33 nm (0.3149 eV) or less. 3. DISCUSSION AND RESULTS 3.1. Validation As shown in Figure 5, the calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the previously synthesized 29 C26H16 cata-condensed PAHs is performed using the mentioned annellation theory technique. The comparison between the available and the calculated locations of maximum absorbance of the p and β bands in the UVVis spectra of the 29 C26H16 cata-condensed PAHs is shown in Figure 6. A special case occurs for compound XXV in which the reported synthesis6 indicates the lack of a purified product for spectral characterization because of secondary oxidation reactions. Although the locations of maximum absorbance of the p and β bands in the UV-Vis spectrum of XXV have been calculated in Figure 5, due to this synthesis uncertainty, the reported locations of maximum absorbance of the p and β bands for XXV have not been taken into account in Figure 6 and in the subsequent statistical comparisons. The complete numerical data for Figure 6 are included in the supporting information (Tables S1 and S2). The results demonstrate a satisfactory agreement between the available and the calculated locations for the p bands (p1, p2, and p3); and for the β bands (β1, β2, and β3) with average differences, ̅ ( = available – annellation theory), of +1.5 nm for the p1 bands, -0.2 nm for the p2 bands, +1.4 nm for the p3 bands, -9.0 nm for the β1 bands, 7.2 nm for the β2 bands, and +0.8 nm for the β3 bands, where + or - indicates a higher or lower



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wavelength, respectively, for the location of the available maximum absorbance as compared to the maximum absorbance calculated using the annellation theory technique. A key factor affecting the locations of maximum absorbance of the p and β bands in the UVVis spectra of the C26H16 cata-condensed PAHs calculated with the annellation theory technique is planarity. Planar cata-condensed PAHs I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, and XV present a negligible average difference, ̅, of -0.1 nm for the p bands (average of p1, p2, and p3) and a negligible average difference, ̅, of -2.6 nm for the β bands (average of β1, β2, and β3). On the other hand, nonplanar cata-condensed PAHs XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXXIII, XXXIV, XXXV, and XXXVII present a negligible average difference, ̅, of +2.8 nm for the p bands (average of p1, p2, and p3) and a minor average difference, ̅, of -8.1 nm for the β bands (average of β1, β2, and β3). Thus, the transition from planar to nonplanar in C26H16 cata-condensed PAHs does not alter significantly the average difference between the available and the calculated locations of maximum absorbance of the p bands, but changes to some extent (-5.5 nm) the average difference between the available and the calculated locations of maximum absorbance of the β bands. 3.2. Elucidation Once the annellation theory technique for the calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the C26H16 cata-condensed PAHs is validated using the analysis performed in section 3.1., the technique is used, as described in Figure 7, for the calculation of the locations of maximum absorbance of the p and β bands of the eight C26H16 cata-condensed PAHs (XVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, and XXXVI).


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3.3. Substantiation The ZINDO/S methodology explained in the Theoretical Methods section is applied for the calculation of the locations of maximum absorbance of the p1 and β1 bands of the eight C26H16 cata-condensed PAHs. The results of the application of the ZINDO/S methodology are presented in Figure 8A. The comparison between the calculated locations of maximum absorbance of the p1 and β1 bands in the UV-Vis spectra of the eight cata-condensed PAHs using the annellation theory method and the ZINDO/S methodology is presented in Figure 8B. The comparison indicates average differences ̅ ( = annellation theory – ZINDO/S) of +10 nm and +4 nm in the locations of maximum absorbance of the p1 and β1 bands, where + or - indicates a higher or lower wavelength, respectively, for the location of the maximum absorbance using the annellation theory as compared to the maximum absorbance calculated using the ZINDO/S methodology. The most pronounced effect occurs for XXVIII with differences of +48 nm for the p bands and +19 nm for the β bands. On the other hand, the slightest effect occurs for XXVII with differences of -1 nm for the p bands and -9 nm for the β bands. In addition, the comparison between the annellation theory calculations in Figure 5 and the ZINDO/S calculations for the locations of the p1 and β1 bands in the UV-Vis spectra of the 29 C26H16 cata-condensed PAHs with available reference standards illustrated in the supporting information (Table S3) is consistent with the abovementioned shifts. Average differences ̅ of +16 nm and +10 nm in the locations of maximum absorbance of the p1 and β1 bands are observed. The ZINDO/S theoretical estimates are derived from a single “frozen” molecule in the gas phase at 0 K without corrections for thermal motions and solvent effects. The difference between



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the locations of maximum absorbance of the p1 and β1 bands of the cata-condensed PAHs as calculated using the annellation theory method versus the ZINDO/S methodology, could be due to the Stokes shift, which involves the reconfiguration of the solvent cage for the ground electronic state once the excited PAH molecule undergoes photoemission.34,35 The Stokes shift to the red is reported to be around 10-45 nm for solvents with low polarity. An instructive comparison among the reference standards available, the annellation theory calculations, and the ZINDO/S methodology for the locations of the p1 and β1 bands in the UVVis spectra of the 29 C26H16 cata-condensed PAHs is shown in Figure 9. The complete numerical data for Figure 9 are included in the supporting information (Table S3). The comparison indicates average percent differences of 3% and 5% between the locations of the p1 bands calculated using the annellation theory and the ZINDO/S methodology with respect to the locations of the p1 bands from reference standards. Additionally, there are average percent differences of 4% and 3% between the locations of the β1 bands calculated using the annellation theory and the ZINDO/S methodology with respect to the locations of the β1 bands from reference standards. 3.4. Overlapping During the calculation of the locations of maximum absorbance of the p and β bands in the group of 37 C26H16 cata-condensed PAHs illustrated in Figures 5 and 7, there were cases, e.g., II, XXII, and XXIX, in which the locations of maximum absorbance of one or more of the longest wavelength β bands overlapped the locations of maximum absorbance of one or more of the lowest wavelength p bands. In these cases, it is anticipated that the β bands would prevail over the p bands due to the high β/p absorbance intensity ratio in cata-condensed PAHs (as it was


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stated in the introduction) and thus, only one or two of the most prominent p bands would be observed. 4. CONCLUSIONS Using the annellation theory, the locations of maximum absorbance of the p and β bands in the UV-Vis spectra were calculated for eight C26H16 cata-condensed PAHs, XVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXXII, and XXXVI, for which synthesis procedures are not available. Initially, the annellation theory procedure was validated by comparing the calculated locations of the p and β bands in the UV-Vis spectra with the respective locations of the p and β bands available for 29 isomers in the C26H16 cata-condensed group. The results for 29 of the 37 isomers with available UV-Vis spectra showed satisfactory average differences, ̅, of +1.5 nm for the p1 bands, -0.2 nm for the p2 bands, +1.4 nm for the p3 bands, -10 nm for the β1 bands, -7.2 nm for the β2 bands, and +0.8 nm for the β3 bands. Also, planar cata-condensed PAHs I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, and XV present a negligible average difference, ̅, of -0.1 nm for the p bands (average of p1, p2, and p3) and a negligible average difference, ̅, of -2.6 nm for the β bands (average of β1, β2, and β3). On the other hand, nonplanar cata-condensed PAHs XVII, XVIII, XIX, XX, XXI, XXII, XXIII, XXIV, XXV, XXVI, XXXIII, XXXIV, XXXV, and XXXVII present a negligible average difference, ̅, of +2.8 nm for the p bands (average of p1, p2, and p3) and a minor average difference, ̅, of -8.1 nm for the β bands (average of β1, β2, and β3). With respect to the agreement between the locations of the p and β bands in the UV-Vis spectra of the eight C26H16 cata-condensed PAHs calculated using the annellation theory method and the corresponding locations determined using the ZINDO/S semiempirical calculations, the average differences, ̅, of +10 nm and +4 nm for the p1 and β1 bands



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were acceptable and likely related to the Stokes shift (10 nm to 45 nm to longer wavelengths for solvents with low polarity). As a final point, the locations of the p1 and β1 bands in the UV-Vis spectra of 29 cata-condensed PAHs calculated with the annelation theory and the ZINDO/S methodology are consistent with the locations from reference standards available with average percent differences of 3% (annellation theory) and 5% (ZINDO/S) for the p1 bands, and 4% (annellation theory) and 3% (ZINDO/S) for the β1 bands. This is the first report of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the eight C26H16 cata-condensed isomers dibenzo[c,m]tetraphene, XVI; naphtho[1,2-c]chrysene, XXVII; dibenzo[c,f]tetraphene, XXVIII; benzo[f]picene, XXIX; naphtho[2,1-a]tetraphene,

XXX;

naphtho[2,1-c]tetraphene,

XXXI;

dibenzo[c,l]chrysene,

XXXII; naphtho[1,2-a]tetraphene, XXXVI. The characterization of PAHs with unknown synthesis procedures using the annellation theory will support current experimental efforts to understand asphaltenes structure. Petroleum asphaltenes are polycyclic aromatic compounds similar to polycyclic aromatic hydrocarbons (PAHs) but containing heteroatoms (N, O, S) and alkyl side chains in their structure. The elucidation of asphaltene structures is fundamental to be able to understand their interfacial chemistry. There has been a long standing debate about asphaltenes structure and architecture. Very recently based on advanced imaging technique Schuler et al36 have presented AFM images of 100 asphaltene molecules, including coal and some oil asphaltenes; which represented major advance in the understanding of asphaltene structures. Crude oil and asphaltene absorption spectra exhibit similar properties, and the PAHs in heavier crude oils and asphaltenes are known to be the source of the color of heavy oils.37-41 Therefore, understanding the electronic bands of PAHs is becoming increasingly important. The optical properties of asphaltenes is of significant 14 ACS Paragon Plus Environment

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importance to obtain a better understanding of their structure and therefore of their surface activity as stabilizers of oil-water emulsions. Also, enhance oil recovery requires disrupting the wettability of the oil-mineral surface. Asphaltenes play a major role in the oil-mineral interfacial chemistry. Understanding their structure is fundamental to be able to understand their interfacial chemistry. ASSOCIATED CONTENT Supporting Information Names corresponding to the PAH structures analyzed in the article, calculated and available locations of maximum absorbance of the p1, p2, p3, β1, β2, and β3 bands in the UV-Vis spectra of 29 C26H16 cata-condensed PAHs, and comparison among the reference standards available, the annellation theory calculations, and the ZINDO/S methodology for the locations of the p1 and β1 bands in the UV-Vis spectra of 29 C26H16 cata-condensed PAHs. AUTHOR INFORMATION Corresponding Author *Guest Researcher, National Institute of Standards and Technology, NIST, 100 Bureau Drive, Mail Stop 8390, Gaithersburg, Maryland 20899. E-mail: [email protected]. Author Contributions The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript. Notes



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The authors declare no competing financial interest. Certain commercial equipment, instruments, or materials (or suppliers, or software, ...) are identified in this paper to foster understanding. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology, NIST, nor does it imply that the materials or equipment identified are necessarily the best available for the purpose. ABBREVIATIONS IUPAC, International Union of Pure and Applied Chemistry REFERENCES (1) Sander LC, Wise SA (1997) NIST Special Publication 922: Polycyclic Aromatic Structure Index. National Institute of Standards and Technology, Gaithersburg, USA (2) Clar, E. Polycyclic Hydrocarbons; Academic Press: New York, 1964. (3) Oña-Ruales, J. O.; Ruiz-Morales, Y. Extended Y-Rule Method for the Characterization of the Aromatic Sextets in Cata-Condensed Polycyclic Aromatic Hydrocarbons. J. Phys. Chem. A 2014, 118, 12262-12273. (4) Sharma, A. K.; Amin, S. Synthesis and Identification of Major Metabolites of Environmental Pollutant Dibenzo[c,mno]Chrysene. Chem. Res. Toxicol. 2005, 18, 1438-1443. (5) Sharma, A. K.; Lin, J. M.; Desai, D.; Amin, S. Convenient Syntheses of Dibenzo[c,p] Chrysene and its Possible Proximate and Ultimate Carcinogens: In Vitro Metabolism and DNA Adduction Studies. J. Org. Chem. 2005, 70, 4962-4970.


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(6) Laarhoven, W. H.; Cuppen, T. H. J. H. M., Nivard, R. J. F. Photodehydrocyclizations in Stilbene-Like Compounds—III: Effect of Steric Factors. Tetrahedron 1970, 26, 4865-4881. (7) Clar, E.; McAndrew, B. A.; Stephen, J. F. The Electronic Interaction in Benzologues of Pyrene. Tetrahedron 1970, 26, 5465-5478. (8) Tinnemans, A. H. A.; Laarhoven, W. H. Photodehydrocyclizations in Stilbene-Like Compounds. X. Rearrangements in the Photocyclization of 4, 5-Diphenyltriphenylene and 4, 5Diphenylphenanthrene. J. Am. Chem. Soc. 1974, 96, 4617-4622. (9) Brison, J.; Martin, R. H. Synthèse, Par la Méthode de Hewett, Des Benzo[a]Naphto[2, 1‐j] Anthracéne, Naphto[2,1‐c]Chrysene, Benzo[a]Picéne et 8,16‐Diméthoxycarbonylbenzo[c]Naphto[2,1‐1]Chrysene. B. Soc. Chim. Belg. 1983, 92, 893-899. (10) Grellmann, K. H.; Hentzschel, P.; Wismontski-Knittel, T.; Fischer, E. The Photophysics and Photochemistry of Pentahelicene. J. Photochem. 1979, 11, 197-213. (11) Fetzer, J. C. Large (C ≥ 24) Polycyclic Aromatic Hydrocarbons: Chemistry and Analysis; WileyInterscience: New York, 2000.

(12) Oña-Ruales, J. O.; Ruiz-Morales, Y. The Predictive Power of the Annellation Theory: The Case of the C32H16 Benzenoid Polycyclic Aromatic Hydrocarbons. J. Phys. Chem. A 2014, 118, 5212-5227. (13) Angliker, H.; Rommel, E.; Wirz, J. Electronic Spectra of Hexacene in Solution (Ground State. Triplet State. Dication and Dianion). Chem. Phys. Lett. 1982, 87, 208-212. (14) Lang, K. F. Pure Products from Coal Tar. Angew. Chem-Ger. Edit. 1951, 63, 345-349.



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Page 18 of 40

(15) Clar, E.; Kelly, W. 2: 3-Benzopicene and Naphtho(2′:3′-1:2) chrysene. J. Chem. Soc. 1957, 4163-4166. (16) Marsili, A. Condensation of 2-Benzoylbenzoic with 2-Naphthylacetic Acid and Synthesis of Benzo[a]Pentaphene. J. Org. Chem. 1967, 32, 240-241. (17) Cerius 2, version 4.6, Accelrys Inc.: San Diego, CA, 2001 (18) Sun , H.; Ren, P.; Fried, J. R. The COMPASS Force Field: Parameterization and Validation for Polyphosphazenes. Comput. Theor. Polym. Sci. 1998, 8, 229-246. (19) Sun, H. COMPASS: An Ab Initio Force-Field Optimized for Condensed-Phase Applications-Overview with Details on Alkane and Benzene Compounds. J. Phys. Chem. B 1998, 102, 7338-7364. (20) Correa de Mello, P.; Hehenberger, M.; Zerner, M. C. Converging SCF Calculations on Excited States. Int. J. Quantum Chem. 1982, 21, 251-258. (21) Ruiz-Morales, Y. HOMO−LUMO Gap as an Index of Molecular Size and Structure for Polycyclic Aromatic Hydrocarbons (PAHs) and Asphaltenes: A Theoretical Study. I. J. Phys. Chem. A 2002, 106, 11283-11308. (22) Somers, M. L.; Wornat, M. J. UV Spectral Identification of Polycyclic Aromatic

Hydrocarbon Products of Supercritical 1-Methylnaphthalene Pyrolysis. Polycycl. Aromat. Comp. 2007, 27, 261-280. (23)

Erünlü, R. K. Synthesen von Benzo‐Naphtho‐Phenalenen und Benzo‐Naphtho‐

Pyrenen. Chem. Ber. 1965, 98, 743-755.


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(24) Zander, M.; Franke, W. H. Mehrkernige Aromatische Systeme Durch Diensynthesen mit Chrysenchinon‐(2.8). Chem. Ber. 1968, 101, 2404-2408. (25) Friedel, R. A.; Orchin, M. Ultraviolet Spectra of Aromatic Compounds. Wiley: New York, 1952. (26) Masonjones, M. C. Kinetic Control of Polyaryl Formation in a Pyrolysis Environment. Diss. Massachusetts Institute of Technology, 1995. (27) Anderson, D. M. W.; Campbell, N.; Leaver, D.; Stafford, W. H. Syntheses of 1Phenylfluorene and 1-and 3-Phenylphenanthrene. J. Chem. Soc. 1959, 3992-3997. (28) Babayan, V. O.; Zagorets, P. A.; Tatevosyan, G. T. Synthesis of Hydrocarbons of 1,2Benzanthracene Series. Zh Obshch Khim+ 1953, 23, 1214-1220. (29) Clar, E.; Guye-Vuilleme, J. F.; Stephen, J. F. Higher Annellated 1:2,7:8Dibenzochrysenes. Tetrahedron 1964, 20, 2107-2117. (30) Friedel, R. A.; Orchin, M.; Reggel, L. Steric Hindrance and Short Wave Length Bands in the Ultraviolet Spectra of Some Naphthalene and Diphenyl Derivatives. J. Am. Chem. Soc. 1948, 70, 199-204. (31) Zander, M.; Franke, W. H. 1.12; 4.5‐Dibenzo‐Perylen und 1.12‐Benzo‐[Naphtho‐2″″.3′′:4.5‐ Perylen].Chem. Ber. 1966, 99, 1275-1278. (32) Blümer, G. P.; Gundermann, K. D.; Zander, M. Zur Umsetzung von Polycyclischen Aromatischen Kohlenwasserstoffen mit Benzol und Aluminiumchlorid. Chem. Ber. 1976, 109, 1991-2000.



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(33) Vingiello, F. A.; Henson, P. D. 7-Phenyldibenz[a,h]anthracene and Benzo[e]Naphtho[1,2b]pyrene. J. Org. Chem. 1965, 30, 2842-2845. (34) Berlman, I. B. Handbook of Fluorescence Spectra of Aromatic Molecules; Academic Press: New York, 1971. (35) Lakowicz, J. R. Principles of Fluorescence Spectroscopy. Springer: New York, 2006. (36) Schuler, B.; Meyer, G.; Peña, D.; Mullins, O. C.; Gross, L. Unraveling the Molecular Structures of Asphaltenes by Atomic Force Microscopy. J. Am. Chem. Soc., 2015, 137, 98709876. (37) Ruiz-Morales, Y.; Mullins, O. C. Singlet–Triplet and Triplet–Triplet Transitions of Asphaltene PAHs by Molecular Orbital Calculations. Energy Fuels. 2013, 27, 5017-5028. (38) Klee, T.; Masterson, T.; Miller, B.; Barrasso, E.; Bell, J.; Lepkowicz, R.; West, J.; Haley, J. E.; Schmitt, D. L.; Flikkema, J. L.; et al. Triplet Electronic Spin States of Crude Oils and Asphaltenes. Energy Fuels. 2011, 25, 2065-2075. (39) Ruiz-Morales, Y.; Mullins, O. C. Polycyclic Aromatic Hydrocarbons of Asphaltenes Analyzed by Molecular Orbital Calculations with Optical Spectroscopy. Energy Fuels. 2007, 21, 256-265. (40) Alvarez-Ramírez, F.; Ruiz-Morales, Y. Island versus Archipelago Architecture for Asphaltenes: Polycyclic Aromatic Hydrocarbon Dimer Theoretical Studies. Energy Fuels. 2013, 27, 1791-1808.


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(41) Juyal, P.; McKenna, A. M.; Yen, A.; Rodgers, R. P.; Reddy, C. M.; Nelson, R. K.; Andrews, A. B.; Atolia, E.; Allenson, S. J.; Mullins, O. C.; et al. Analysis and Identification of Biomarkers and Origin of Color in a Bright Blue Crude Oil. Energy Fuels. 2010, 25, 172-182.


IV

XXI

XVII

XXVI

XXII

XVIII

XXVII

XXIII

XIX

XXXII

XXVIII

XXIV

XX

XXXV

XXXIII

XXXVI

XXXIV

Group 4

III

VII

XXV

XXXI

Group 3

II

VI

X

XXX

Group 2

V

IX

XXIX

Group 5 XXXVII

ACS Paragon Plus Environment

Group 1 I

VIII

XIII

XVI

XII

XV

XI

XIV

Figure 1. The C26H16 cata-condensed benzenoid PAHs classified according to the absence or presence of bay, cove, fjord, and helical regions. Group 1: Absence of bay, cove, fjord, or helical regions; Group 2: Presence of only bay regions; Group 3: Presence of 1 or 2 cove regions and 0, 1, or 2 bay regions; Group 4: Presence of 1 fjord region and 0, 1, or 2 bay regions; and Group 5: Presence of 1 helical region. The locations, number, and migrating behavior of the sextets in the PAHs I, XIX, XXV, XXXII, XXXVI, and XXXVII have been achieved by means of the information provided in reference 2. The locations, number, and migrating behavior of the sextets in the PAHs II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV, XV, XVI, XVII, XVIII, XX, XXI, XXII, XXIII, XIV, XXVI, XXVII, XXVIII, XXIX, XXX, XXXI, XXXIII, XXXIV, and XXXV have been achieved by means of the Extended Y-rule method.3 The structures in black denote the compounds with known UV-Vis spectra and the structures in red denote the compounds with unknown UV-Vis spectra. The complete list of names for the PAH structures is included in the supplementary information section (Figure S1). The black lines connecting rings denote the movement of the aromatic sextets.

22

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 40 The Journal of Physical Chemistry

Page 23 of 40

Log2 of Absorbance 1000

100

10

1 200

β bands

250

p bands

300

Wavelength, nm

α bands

350

Figure 2. The UV-Vis spectrum of XXXVIII (pyrene). The symbols β, p, and α were given by Clar2 to characterize the UV-Vis spectral bands of PAHs.

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60




1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Page 24 of 40

Page 25 of 40

PAH 2

λp, nm p1111 p2222 p3333

λβ, nm β1111 β2222 β3333

UV-Vis

UV-Vis

PAH 1

λp, nm λβ, nm p111 β111 p222 β222 p333 β333

p1= ( p111 - p1111 ) + p11 p2= ( p222 – p2222 ) + p22 p3= ( p333 – p3333 ) + p33

β1= ( β111 - β1111 ) + β11

PAH 4

λp, nm λβ, nm p11 β11 p22 β22 p33 β33

UV-Vis

PAH 3 UV-Vis

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


β2= ( β222 – β2222 ) + β22

λp, nm λβ, nm p1 β1 p2 β2 p3 β3

β3= ( β333 – β3333 ) + β33

Figure 4. Annellation theory method introduced in reference 12 for the prediction of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the pericondensed PAHs C32H16. Red line denotes structural and aromatic enclosure. Black line denotes structural and aromatic relationship.



λp, nm λβ, nm 471 441 415

274 265

λp, nm λβ, nm

λp, nm λβ, nm

359 344 329

290 280 267

UV-Vis2

252

UV-Vis2

375 355 338

B. UV-Vis Bands Predicted for II

UV-Vis2

λp, nm λβ, nm

UV-Vis2

UV-Vis2

A. UV-Vis Bands Predicted for I

λp, nm λβ, nm 350 335 322

325

326 312 299

UV-Vis11

UV-Vis2

444 416 392

λp, nm λβ, nm 475 443 416

315 302 290

λp, nm λβ, nm 347 324 336 311 322 303

D. UV-Vis Bands Predicted for IV

C. UV-Vis Bands Predicted for III

λp, nm λβ, nm

356 345 329

UV-Vis

678 624 580

354 337 318

λp, nm λβ, nm

λp, nm λβ, nm

381 362 345

308 295

UV-Vis2

303

UV-Vis22

582 538 503

λp, nm λβ, nm 350 335 322

λp, nm λβ, nm 360 342 328

315 299 275

377 358 342

318 304 292

UV-Vis

287 274 256

UV-Vis

329 315 304

299 289 280

IV

III λp, nm λβ, nm

299 289 280

II

λp, nm λβ, nm

UV-Vis23

λp, nm λβ, nm

UV-Vis

UV-Vis2

I

UV-Vis2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 40

λp, nm λβ, nm 346 331 319

309 298

Figure 5. Calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the 29 C26H16 cata-condensed PAHs using the annellation theory method of Figure 4. The black lines connecting rings denote the movement of the aromatic sextets.


F. UV-Vis Bands Predicted for VI

378 360 343

307 295

λp, nm λβ, nm 373 355 345

UV-Vis2

λp, nm λβ, nm

UV-Vis24

UV-Vis2

E. UV-Vis Bands Predicted for V

336 322

λp, nm λβ, nm 375 355 338

252

λp, nm λβ, nm 359 344 329

335 320

UV-Vis2

UV-Vis2

λp, nm λβ, nm

458 431 406

λp, nm λβ, nm 450 435 423

319 306

337 322 310

λp, nm λβ, nm

λp, nm λβ, nm

458 431 406

335 320

357 351 348

437 414 392

357

λp, nm λβ, nm 516 480 450

325 311 290

VIII

λp, nm λβ, nm 307 290

365 347 331

305 288 280

UV-Vis

305 288 280

UV-Vis

VII

365 347 331

λp, nm λβ, nm

H. UV-Vis Bands Predicted for VIII

G. UV-Vis Bands Predicted for VII

λp, nm λβ, nm

453 425 401

UV-Vis

315 302

UV-Vis2

344 328 323

UV-Vis2

286 275 265

λp, nm λβ, nm

UV-Vis2

349 333 321

290 280 267

VI

λp, nm λβ, nm

UV-Vis2

λp, nm λβ, nm

UV-Vis

UV-Vis2

V

UV-Vis2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


UV-Vis2

Page 27 of 40

λp, nm λβ, nm 423 396 375

295 279

Figure 5 (Continued). Calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the 29 C26H16 cata-condensed PAHs using the annellation theory method of Figure 4. The black lines connecting rings denote the movement of the aromatic sextets.



321 309 297

λp, nm λβ, nm 442 415 393

356 339 323

λp, nm λβ, nm 458 431 406

335 320

UV-Vis2

345 328

J. UV-Vis Bands Predicted for X

UV-Vis2

λp, nm λβ, nm

UV-Vis2

UV-Vis2

I. UV-Vis Bands Predicted for IX

λp, nm λβ, nm 541 504 472

λp, nm λβ, nm 446 420

321 305 291

λp, nm λβ, nm 475 443 416

UV-Vis2

326 312 299

UV-Vis11

UV-Vis2

444 416 392

453 425 401

319 306

354 337 318

λp, nm λβ, nm 458 431 406

335 320

360 342 328

315 299 275

λp, nm λβ, nm 453 425 401

319 306

UV-Vis

λp, nm λβ, nm

UV-Vis2

287 274 256

UV-Vis

329 315 304

536 498 467

366 349

λp, nm λβ, nm 450 435 423

337 322 310

XII

XI λp, nm λβ, nm

λp, nm λβ, nm

L. UV-Vis Bands Predicted for XII

K. UV-Vis Bands Predicted for XI

λp, nm λβ, nm

λp, nm λβ, nm

UV-Vis

286 275 265

UV-Vis2

349 333 321

382 363 344

X

UV-Vis2

λp, nm λβ, nm

UV-Vis

UV-Vis2

IX

UV-Vis2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 40

λp, nm λβ, nm 445 429 418

321 308



N. UV-Vis Bands Predicted for XIV

458 431 406

335 320

λp, nm λβ, nm 541 504 472

UV-Vis25

λp, nm λβ, nm

UV-Vis2

UV-Vis2

M. UV-Vis Bands Predicted for XIII

382 363 344

λp, nm λβ, nm 306

254

352 331

λp, nm λβ, nm 363 346 331

UV-Vis2

261 242

UV-Vis28

UV-Vis27

302 280

315 302 290

299 290

λp, nm λβ, nm 284 273

257 249

412 404

342 338

λp, nm λβ, nm 334 321 308

286 277

UV-Vis

λp, nm λβ, nm

UV-Vis2

304 290

UV-Vis

351 338 324

309 297


370

λp, nm λβ, nm 334 321 308

286 277

XVII

XV λp, nm λβ, nm

388 368 351

P. UV-Vis Bands Predicted for XVII

O. UV-Vis Bands Predicted for XV

λp, nm λβ, nm

356 345 329

UV-Vis

448 420 397

λp, nm λβ, nm

UV-Vis2

305 288 280

λp, nm λβ, nm

UV-Vis2

365 347 331

UV-Vis

UV-Vis2

λp, nm λβ, nm

λp, nm λβ, nm

XIV

XIII

UV-Vis2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


UV-Vis26

Page 29 of 40

λp, nm λβ, nm 384 369

315 305




290 280 267

λp, nm λβ, nm 372 354 338

UV-Vis2

359 344 329

UV-Vis2

UV-Vis2

λp, nm λβ, nm

308 295 284

λp, nm λβ, nm 359 344 329

290 280 267

UV-Vis2

R. UV-Vis Bands Predicted for XIX

Q. UV-Vis Bands Predicted for XVIII

362 343 330

304 290 282

357 342 327

306 295

λp, nm λβ, nm 334 321 308

453 425 401

319 306

286 277

λp, nm λβ, nm 359 344 329

290 280 267

λp, nm λβ, nm 351 339

294 283

λp, nm λβ, nm 350 335 322

299 289 280

UV-Vis

314 301 290

308 295 284

λp, nm λβ, nm 466 337 435 321 410

λp, nm λβ, nm 372 354 338

308 295 284

XXI

UV-Vis2

374 360

UV-Vis

XX λp, nm λβ, nm

372 354 338

T. UV-Vis Bands Predicted for XXI

UV-Vis2

λp, nm λβ, nm

UV-Vis2

UV-Vis

S. UV-Vis Bands Predicted for XX

λp, nm λβ, nm

UV-Vis

λp, nm λβ, nm

UV-Vis2

286 275 265

UV-Vis2

349 333 321

UV-Vis

UV-Vis2

λp, nm λβ, nm

λp, nm λβ, nm

XIX

XVIII

UV-Vis29

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 30 of 40

λp, nm λβ, nm 363 345 331

317 304 297



395 374 355

297 290 269

V. UV-Vis Bands Predicted for XXIII

λp, nm λβ, nm 393 373 354

UV-Vis2

λp, nm λβ, nm

UV-Vis2

UV-Vis

U. UV-Vis Bands Predicted for XXII

338 322

λp, nm λβ, nm 315 303 296

281 272

327 309

293 281 274

251 242

λp, nm λβ, nm 315 303 296

286 277

281 272

λp, nm λβ, nm 288 282 272

226 219 213

351 337 326

317 304

λp, nm λβ, nm 372 354 338

308 295 284

UV-Vis

λp, nm λβ, nm

UV-Vis2

287 274 256

UV-Vis

329 315 304

308 295 284

λp, nm λβ, nm 391 372 350

313 300

λp, nm λβ, nm 383 364 346

300

XXV

XXIV λp, nm λβ, nm

372 354 338

X. UV-Vis Bands Predicted for XXV

UV-Vis30

λp, nm λβ, nm

UV-Vis2

UV-Vis2

W. UV-Vis Bands Predicted for XXIV

334 321 308

UV-Vis

332 320 307

λp, nm λβ, nm

UV-Vis26

286 277

λp, nm λβ, nm

UV-Vis2

334 321 308

UV-Vis

UV-Vis2

λp, nm λβ, nm

λp, nm λβ, nm

XXIII

XXII

UV-Vis2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


UV-Vis2

Page 31 of 40

λp, nm λβ, nm 467 436 412

382




251 242

λp, nm λβ, nm 315 303 296

281 272

λp, nm λβ, nm 388 367 348

303 292

UV-Vis2

293 281 274

Z. UV-Vis Bands Predicted XXXIII

UV-Vis2

λp, nm λβ, nm

UV-Vis2

UV-Vis2

Y. UV-Vis Bands Predicted for XXVI

373 360 346

334 320

388 367 348

303 292

λp, nm λβ, nm 407 384 364

310 300

333 318 305

λp, nm λβ, nm 388 367 348

303 292

348

340 326


310 300

UV-Vis

310 300

310 297


317 305

λp, nm λβ, nm 418 394 373

311 298 272

XXXV

λp, nm λβ, nm

UV-Vis2

329

UV-Vis

XXXIV λp, nm λβ, nm

378 359 343

AB. UV-Vis Bands Predicted XXXV

UV-Vis2

λp, nm λβ, nm

UV-Vis31

UV-Vis2

AA. UV-Vis Bands Predicted XXXIV

329

UV-Vis

304 290

λp, nm λβ, nm

UV-Vis2

351 338 324

λp, nm λβ, nm

XXXIII

λp, nm λβ, nm

UV-Vis2

λp, nm λβ, nm

UV-Vis

UV-Vis2

XXVI

UV-Vis2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 32 of 40

λp, nm λβ, nm 359 318 306



λp, nm λβ, nm 293 281 274

251 242

UV-Vis2

AC. UV-Vis Bands Predicted XXXVII

UV-Vis2

λp, nm λβ, nm 315 303 296

281 272

XXXVII λp, nm λβ, nm 329

310 300

UV-Vis

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


UV-Vis2

Page 33 of 40


340 330




700

p1

650

Wavelength, nm

600 550 500 450 400 350

700

I II III IV V VI VII VIII IX X XI XII XIII XIV XV XVII XVIII XIX XX XXI XXII XXIII XXIV XXV XXVI XXXIII XXXIV XXXV XXXVII

300

650

p2

Wavelength, nm

600 550 500 450 400 350

700


300

650

p3

600 550 500 450 400 350 300


Wavelength, nm

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 34 of 40

C26H16 cata-condensed PAH

Figure 6. Comparison between available UV-Vis spectra values (red lines) and those calculated using the annellation theory method of Figure 4 (black bars) for corresponding locations of maximum absorbance of the p bands (p1, p2, and p3) and β bands (β1, β2, and β3) of the 29 C26H16 cata-condensed PAHs.


Page 35 of 40

450

β1 Wavelength, nm

400

350

300

250

450


200

β2

Wavelength, nm

400

350

300

250

450


200

400

β3

350

300

250

200


Wavelength, nm

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60



Figure 6 (Continued). Comparison between available UV-Vis spectra values (red lines) and those calculated using the annellation theory method of Figure 4 (black bars) for corresponding locations of maximum absorbance of the p bands (p1, p2, and p3) and β bands (β1, β2, and β3) of the 29 C26H16 cata-condensed PAHs.



251 242

λp, nm λβ, nm 319 306 295

λp, nm λβ, nm

UV-Vis2

293 281 274

UV-Vis2

UV-Vis2

λp, nm λβ, nm

267 259

293 281 274

251 242

UV-Vis2

B. UV-Vis Bands Predicted for XXV

A. UV-Vis Bands Predicted for XXVI

320 307

λp, nm λβ, nm 447 420 397

UV-Vis22

307 295

UV-Vis32

UV-Vis2

378 360 343

293 281 261

340 323

λp, nm λβ, nm 381 362 345

308 295

418 393 375

319 303

λp, nm λβ, nm 329 315 304

287 274 256

UV-Vis

λp, nm λβ, nm

UV-Vis2

286 275 265

UV-Vis

349 333 321

267 259

λp, nm λβ, nm 347 331

309 298

λp, nm λβ, nm 390 336

319 307 275

XXIX

XXVIII λp, nm λβ, nm

319 306 295

D. UV-Vis Bands Predicted XXIX

C. UV-Vis Bands Predicted XXVIII

λp, nm λβ, nm

321 306

UV-Vis

377 363 345

λp, nm λβ, nm

UV-Vis33

304 290

λp, nm λβ, nm

UV-Vis2

351 338 324

UV-Vis

UV-Vis2

λp, nm λβ, nm

λp, nm λβ, nm

XXVII

XVI

UV-Vis2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 36 of 40


298 286

295

Figure 7. Calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the eight C26H16 cata-condensed PAHs with no UV-Vis spectra available using the annellation theory method of Figure 4. The black lines connecting rings denote the movement of the aromatic sextets.


302 280

261 242

F. UV-Vis Bands Predicted for XXXI

λp, nm λβ, nm 363 346 331

UV-Vis2

λp, nm λβ, nm

UV-Vis28

UV-Vis27

E. UV-Vis Bands Predicted for XXX

299 290

λp, nm λβ, nm 319 306 295

267 259

332 329

293 281 274

251 242

λp, nm λβ, nm 315 303 296

305 288 280

281 272 229

λp, nm λβ, nm 293 281 274

251 242


310 300

UV-Vis

λp, nm λβ, nm 343 323 328 311

UV-Vis2

293 281 261

UV-Vis

321 306

293 281 261

λp, nm λβ, nm 367 331 347 310

λp, nm λβ, nm 359 344 329

290 280 267

XXXVI

XXXII λp, nm λβ, nm

321 306

H. UV-Vis Bands Predicted XXXVI

UV-Vis2

λp, nm λβ, nm

UV-Vis2

UV-Vis2

G. UV-Vis Bands Predicted XXXII

365 347 331

UV-Vis

383 372

λp, nm λβ, nm

UV-Vis2

293 281 261

λp, nm λβ, nm

UV-Vis2

321 306

UV-Vis

UV-Vis2

λp, nm λβ, nm

λp, nm λβ, nm

XXXI

XXX

UV-Vis2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


UV-Vis2

Page 37 of 40


349 338

Figure 7 (Continued). Calculation of the locations of maximum absorbance of the p and β bands in the UV-Vis spectra of the eight C26H16 cata-condensed PAHs with no UV-Vis spectra available using the annellation theory method of Figure 4. The black lines connecting rings denote the movement of the aromatic sextets.



A. nm

p1

β1

p1

β1

p1

β1

p1

β1

p1

β1

p1

β1

p1

β1

p1

β1

357

315

348

318

370

300

346

306

369

327

372

319

352

315

378

347

XVI

XXVII

XXVIII

XXIX

XXX

XXXI

XXXII

XXXVI

B. p1 band from Annellation Theory

β1 band from Annellation Theory

p1 band from ZINDO/S

β1 band from ZINDO/S

430

360

410

350

Wavelength, nm

Wavelength, nm

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 38 of 40

390 370 350 330 310

340 330 320 310 300 290

290

280

270

270



Figure 8. A. Locations of maximum absorbance of the p1 and β1 bands of the eight cata-condensed C26H16 PAHs with unknown UV-Vis spectra calculated using the ZINDO/S methodology. B. Comparison of the locations of maximum absorbance of the p1 and β1 bands of the eight catacondensed C26H16 PAHs with unknown UV-Vis spectra calculated using the annellation theory procedure shown in Figure 7 (black bars) and the ZINDO/S methodology (green bars). The complete list of names for the PAH structures is included in the supplementary information section (Figure S1). The black lines connecting rings denote the movement of the aromatic sextets.


Page 39 of 40

700 650

p1 bands

Wavelength, nm

600 550 500 450 400 350 300


250

450

β1 bands 400

350

300

250


Wavelength, nm

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60



Figure 9. Comparison of the locations of the p1 bands (top) and β1 bands (bottom) in the UV-Vis spectra of the 29 C26H16 cata-condensed PAHs using reference standards available (red crosses), the annellation theory calculations (black diamonds), and the ZINDO/S methodology (green squares).



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

TABLE OF CONTENTS GRAPHIC

THE PREDICTIVE POWER OF THE ANNELLATION THEORY


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The Predictive Power of the Annellation Theory: The Case of the

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