Anharmonic Force Field of N2O. Attila G. Csaszar. J. Phys. Chem. , 1994, 98 (36), pp 8823â8826. DOI: 10.1021/j100087a001. Publication Date: September ...
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Physical Chemistry ___________
0 Copyright 1994 by the American Chemical Society
VOLUME 98, NUMBER 36, SEPTEMBER 8,1994
LETTERS Anharmonic Force Field of N20 Attila G . Cshszhr Department of Theoretical Chemistry, Eotvos University, H-I 518 Budapest 1 12, P.O.Box 32, Hungary Received: March 8, 1994; In Final Form: May 30, 1994"
The anharmonic force field of N20 has been determined from high-quality a b initio calculations. The results suggest that among the available experimental sextic force fields the field obtained by algebraic contact transformation is the most reliable, although even in this experimental field most higher-order terms (especially at fifth and sixth order) appear to be phenomenological in nature, i.e., d o not directly correspond to the associated derivatives of the potential energy surface. The accuracy of computed force fields has further been demonstrated by anharmonic force field calculations on the diatomics % lZiNz and % 211 NO.
To the author's knowledgeN20is the only polyatomic molecule Ab initio studies of anharmonic force fields of small polyatomic molecules, including linear molecules,14 symmetric t ~ p ~ and , ~ , ~ besides - ~ ~ C02 for which experimental attempts have been made to asymmetric top~,~-lOproved unambiguously that (a) most determine the complete anharmonic force field through sixth calculated cubic and quartic force constants show reasonably order. These attempts includevarious approaches: (a) numerical, small variation with respect to basis set extension and treatment algebraic contact transformation;Il (b) second-order perturbation of electron correlation; (b) particularly accurate ab initio force theory;12 and (c) direct numerical d i a g ~ n a l i z a t i o n . ~ While ~J~ fields can be obtained if methods incorporating a large portion the early studies1laJ2relied upon vibrational data only, the more of the electron correlation energy with extended basis sets are recent investigationsllb,13,14 employed both vibrational band used; (c) a substantial part of the discrepancy between force centers and rotational band constants during the fit of the constants calculated a t theoretical stationary points and force anharmonic force field. A recent a b initio study2 on the sextic constants obtained from experiments comes from the differences force field of CO2 suggested that, even for this molecule, where in the underlying reference geometries;lb thus, shifting the the complete sextic force field in internal coordinates contains theoretical reference geometry close to the true equilibrium only 28 independent terms, most quintic and sextic constants geometry results in force constants which are in dramatically determined experimentally seem to be completely phenomenobetter agreement with their experimental counterparts; (d) some logical in nature. It seemed to be of interest to compare the of the higher-order experimental constants (especially the quintic anharmonic force fields of N20 determined experimentally to and sextic ones) are phenomenological in nature,2 i.e.,not directly accurate a b initio fields in order to check whether for this molecule, correspondent with the associated derivatives of the potential where the complete internal coordinate sextic force field contains energy surface; and (e) while there is a delicate balance between considerably more, altogether 47, independent constants,lS the approximate electronic energy and exact nuclear-nuclear problems in the experimental force fields similar to those in C02 repulsion energy ( VN)derivative terms of opposite sign, for higherexisted. Therefore, the present communication describes, for order force constants the contributions of the derivatives of VN the first time, the a b initio determination of the complete sex$ become increasingly dominant, resulting in more accurately force field of N 2 0 and, for purposes of comparison, those of X calculated values. 1Z; N2 and 22 l l NO. Note that the complete quartic force field of N 2 0 has been determined previously at several theoretical 0 Abstract published in Aduance ACS Abstracts, August 15, 1994. 0022-3654/94/2098-8823$04.50/0
0 1994 American Chemical Society
The Journal of Physical Chemistry, Vol. 98, No. 36, 1994
TABLE 1: Theoretical and Experimental Sextic Force Fields and Molecular Constants for 3 'C: N2, Calculated at r, = 1.097 685 Aa CC-PVTZ CC-pVQZ exptlb param SCF CCSD CCSD(T) SCF CCSD CCSD(T) RKR SP 0.8501(0.8892) 25.00(24.72) fill -172.7(-171.3) filii 1003.9(993.5) fi 1I I I -6057.2(-5963.8) ~ I I I I I I 40685(41 340) rec 1.0671(1.0655) wed 2461.6(2447.5) a/ 0.0149(0.0150) w e d 11.86(12.00) fl
a The force cosntants,f, are given in units of aJ A+, where n is the order of the constant. The numbers reported in parentheses were obtained with completely uncontracted basis sets polarized into the core region with two tight (d,f) manifolds (for details see text) and no orbitals frozen. b The potential function whose derivatives are reported as RKR values here was obtained by Allen and Cs6szBrIb by a fit to the RKR data of ref 25. The spectroscopic (SP) values are taken from ref 23. e The optimized bond length, re, given in A, was determined by a fit of a force field through fourth order to five where p is the reduced energy points. The harmonic vibrational frequency, we, given in cm-I, was determined using the formula 1302.7913Cf1/p)~/~, mass in amu. eThe vibrational-rotational constant, ac, given in cm-l, was determined using the formula (-6Be2/we)[1 + 1.05052 X 10-3wJl11/ ( B J I ~ ~ )where ~ / ~ ]Be, (in cm-l) is the equilibrium rotational constant. !The anharmonicity constant, w ~ given , in cm-l, was determined using the formula (0.70241 8/~)(5f1 1 12/fi l2 - 3f1 I I dfi).
TABLE 2 param fl hl fill
fill1 hllll hlllll
re We WCx,
Theoretical Sextic Force Fields and Molecular Constants for 3 211 NO, Calculated at re = 1.150 70 A. cc-pVTZ CC-PVQZ SCF CCSD CCSD(T) SCF CCSD CCSD(T) 0.7 189(0.7395) 17.12(16.86) -127.7(-126.1) 730.5(733.3) -4221.8(-4309.5) 31 278(29 296) 1.1 141(1.1 127) 1972.5(1957.6) 0.0161 (0.0162) 14.14( 14.02)
See footnotes in Table 1. b Reference 24. Not reported due to problems with numerical accuracy. level~.lJ.~The corresponding optimized geometries have been 211 NO have been determined a t the cc-pVTZ, cc-pVQZ, used as reference geometries a t the levels DZP SCF,lb TZ2P CV(TZ), and CV(QZ) SCF, CCSD, and CCSD(T) levels. The SCF,1* TZ2P CISD,la and cc-pVTZ CCSD(T).3 The experiresults obtained are presented in Tables 1 and 2 for N2 and NO, mental geometryllb (re(") = 1.1273 A and &(NO) = 1.1851 respectively. These calculations have been performed, similarly to those for NzO, at the corresponding experimental equilibrium A) has been used as reference a t the DZP SCF, and TZ(2dlf) geometries (re= 1.097 685 Az3and re = 1.150 70 AZ4for N2 and SCF, CCSD, and CCSD(T) 1evels.Ib These a b initio quartic force field studies confirmed the general trends noted above. NO, respectively), so that the effect of geometric shift on the Two basis sets have been selected for this study, the correlationforce constantslb is separated. In the case of NZthe a b initio consistent cc-pVTZ and cc-pVQZ basis sets of Dunning and coresults are compared to RKR values defined as the appropriate workers.16 All 1s core orbitals have been kept frozen in correlated derivatives of a functional form obtained by Allen and C s l s z W level calculations except where noted otherwise. To estimate the through a well-designed fit to RKR points.25 The cc-pVTZ effect of 1s correlation for N2 and NO, the cc-pVTZ and ccCCSD(T) equilibrium bond lengths (re)are about 0.006 A too pVQZ basis sets have been uncontracted and polarized into the long (0.0061 A for N2 and 0.0058 A for NO). These errors core region with two tight (d,f) manifolds in an even-tempered decrease to about 0.0025 8,by extending the basis to cc-pVQZ. manner (multiplying the largest d and f exponents by 3 and 9). Thus, for both diatomics the concentration is about 0.0035 A The resulting basis sets are denoted as CV(TZ) and CV(QZ). upon going from a cc-pVTZ to a cc-pVQZ basis set, in agreement Only the pure spherical components of the basis functions have with the trend reported in ref 3. Furthermore, it is quite interesting been used; thus, for each atom the cc-pVTZ, cc-pVQZ, CV(TZ), to note that the combined effect of 1s correlation and basis set and CV(QZ) basis sets contain 30, 55, 66, and 92 contracted contraction on re is almost the same as the residual error of Gaussian functions (CGFs), respectively. Electronic wave funcCCSD(T) calculations employing uncontracted basis sets; to wit, tions and analytic geometric first derivatives have been determined for N2(NO) the CV(TZ) CCSD(T) re distances differ from in this study at the SCF,17 CCSD,17-19 and CCSD(T)ZO levels. experiment by only -0.0004(0.00007) A, respectively (see Table The complete sextic force fields have been obtained from energy 1). As far as the forceconstants areconcerned, the results obtained points for the diatomics and from analytic first derivatives for for N2 and N O (a) show the steady convergence of theoretical NzO by application of appropriate, carefully selected, symmetric force constant values toward their experimental counterparts as finite-difference formulas.2 No orbitals have been kept frozen, the basis is extended and the level of electron correlation increased due to program limitations, during the cc-pVTZ CCSD(T) and (b) suggest that agreement between theoretical and experigradient calculations. The program systems PSI21 and ACES mental force constants can be substantially improved if the effect 1122 have been used for the a b initi? calculations. The open-shell of 1s correlation26 is included in the theoretical treatment. In CCSD(T) energy calculations for X 2 I I N O employed the ROHFthese two diatomics, 1s correlation engenders the following (re, CCSD(T) methodology of Scuseria.2h ucruexe) shifts (in A, cm-1, cm-1): N2 (-0.002, -8, +0.1) and NO To demonstrate the accuracy of ab initio force-fields a t the (-0.002, -6, +O.l).z7 Furthermore, the results support two levels used in this study, the anharmonic fields of X IZ; Nz and important assertions about cc-pVTZ CCSD(T) force constants a
The Journal of Physical Chemistry, Vol. 98, No. 36, 1994 8825
Theoretical and Experimental Internal Coordinate Anharmonic Force Fields for NzO. theory w-PVTZ CC-PVTZ w-~VTZ const SCF//exptl CCSD(T)//exptl CCSD(T)b ref llb
* Units for the force constants are consistent with energy measured in attojoules, stretching coordinates ( r and R ) in angstroms, and bending coordinates ( a ) in radians. The designation // means "at the geometry of". The abbrevation "exptl" means that the force field was calculated at the = 1.1273 A and re(NO) = 1.1851 A. b Reference 3.
smaller than experiment). Only methods which incorporate a substantial part of electron correlation (CCSD and CCSD(T)) yield quantitatively correct results, especially if large spdfg basis sets are employed. Variances among correlated level force fields seem to be acceptable. These findings are identical to those observed for C02,2 another molecule with cumulenic multiple bonds. In the field of Lacy and Whiffen (LW),*3 obtained by direct numerical diagonalization, frr and fillappear to be too large and too small, respectively. Furthermore, the values of frrrr (52.6 a J A4) andf,,,, (1 232 568 aJ Ad)are too small and too large, respectively, by orders of magnitude. These inaccuracies in the LW diagonal force field could be reflected in the fitted off-diagonalvalues. Indeed, the great majority of the LW quintic and sextic coupling constants are orders of magnitude different from the a b initio constants. Most ab initio higher-order stretchstretch coupling constants are small, usually orders of magnitude smaller than the diagonal ones. Thus, they should safely be
8826 The Journal of Physical Chemistry, Vol. 98, No. 36, 1994 neglected in an empirical fit, as was done by Kobayashi and Suzuki.14 Furthermore, it is interesting to note that the signs of the stretch-stretch coupling constants in higher orders do not seem to follow any simple rule, while the signs of the quadratic and cubic constants can be rationalized using simple arguments.’ The bending modes of N20, similarly to those of CO,,2 appear to be quite harmonic. The diagonal bending constants in fourth and sixth order are rathersmall, asare thestretch-bend interaction constants. Overall, among the experimental fields the TeffoChCdin force field appears to be the most reliable. The conclusions obtained above are basically the same as those obtained for C02;2 most importantly, for both C02 and N2O the force fields obtained by C h a i n using algebraic contact transformation appear to be the most reliable and those obtained by Lacy using direct numerical diagonalization the least reliable, although even in the best experimental field most higher-order terms (especially at fifth and sixth order) appear to be phenomenological in nature, i.e., do not directly correspond to the associated derivatives of the potential energy surface.
Acknowledgment. The research described was partly supported by grants from the Scientific Research Foundation of Hungary (OTKA 2101 and OTKA F013962). The ab initio calculations have been performed on an IBM RS/6000 m560 workstation whose purchase was made possible by a grant from “Catching Up with European Higher Education” (FEFA II/265). The author thanks one of the referees for several useful comments. References and Notes (1) (a) Allen, W. D.; Yamaguchi, Y.; CsPszlr, A. G.; Clabo, D. A., Jr.; Remington, R. B.; Schaefer, H. F., 111. Chem. Phys. 1990, 145, 427. (b) Allen, W. D.; CsPszPr, A. G. J . Chem. Phys. 1993,98,2983. (c) Allen, W. D.; East, A. L. L.; CsPszPr, A. G. Structures and Conformations of NonRigid Molecules; Laane, J., Dakkouri, M., van der Veken, B., Oberhammer, H., Eds.; Kluwer: Dordrecht, 1993. (2) CsPszlr, A. G. J. Phys. Chem. 1992, 96, 7898. (3) Martin, J. M. L.; Taylor, P. R.; Lee, T. J. Chem. Phys. Lett. 1993, 205, 535. (4) Wong, A. T.; Bacskay, G. B. Chem. Phys. Lett. 1993, 207, 360. (5) (a) Martin, J. M. L.; Lee, T. J.; Taylor, P. R. J . Chem. Phys. 1992, 97,8361. (b) Martin, J. M. L.; Lee, T. J. Chem. Phys. Lett. 1992, 200,502. (6) Hargiss, L. 0.;Ermler, W. C. J. Phys. Chem. 1988,92, 300. (7) (a) Gaw, J. F.; Handy, N. C. Chem. Phys. Lett. 1985,121,321. (b) Gaw, J. F.; Handy, N. C. Chem. Phys. Lett. 1986,128, 182. (c) Green, W.
H.; Jayatilaka, D.; Willets, A.; Amos, R. D.; Handy, N. C. J. Chem. Phys. 1990,93,4965. (8) Clabo, D. A., Jr.; Allen, W. D.; Remington, R. B.; Yamaguchi, Y.; Schaefer. H. F.. 111. Chem. Phvs. 1988. 123. 187. (9) (a) Xie; Y.; Boggs, J. E. J . Chem. Phys. 1989, 90,4320. (b) Xie, Y.; Boggs, J. E. J. Chem. Phys. 1989, 91, 1066.
Letters (10) (a) Martin, J. M. L.; Francois, J. P.;Gijbels, R. J. Chem.Phys. 1992, 96, 7633. (b) Martin, J. M. L.; Francois, J. P.; Gijbels, R. J. Chem. Phys. 1992, 97, 3530. (1 1) (a) Chain, A.; Amiot, C.; Cihla, Z . J . Mol. Spectrosc. 1976,63,348. (b) Teffo, J.-L.; Chain, A. J. Mol. Spectrosc. 1989, 135, 389. (12) Suzuki, I. J . Mol. Spectrosc. 1969, 32, 54. (13) Lacy, M.; Whiffen, D. H. Mol. Phys. 1982, 45, 241. (14) Kobayashi, M.; Suzuki, I. J . Mol. Spectrosc. 1987, 125, 24. (15) Note that in linear molecules, due to the presence of degenerate linear
bending vibrations, there are some dependent force constants which need to be included in the power series expansion of the potential2 and are not counted here. (16) (a) Kendall, R. A.; Dunning, T. H., Jr.; Harrison, R. J. J. Chem. Phys. 1992,96,6796. (b) Dunning, T. H., Jr.; Petersen, K. A.; Woon, D. E.; Kendall, R. A. Unpublished. (17) (a) Roothaan, C. C. J. Rev. Mod. Phys. 1951.23.69. (b) Pulay, P. Mol. Phys. 1969, 17, 197. (c) Pulay, P. In Modern Theoretical Chemistry; Schaefer, H. F., 111, Eds.; Plenum Press: New York, 1977; Vol. 4; pp 153185. (d) Hehre, W. J.; Radom, L.; Schleyer, P. v. R.; Pople, J. A. Ab Initio Molecular Orbital Theory;Wiley-Interscience: New York, 1986. (e) Szabo, A.; Ostlund, N. S . Modern Quantum Chemistry;McGraw-Hill: New York, 1989. (18) (a) Cizek, J. J. Chem.Phys. 1966,45,4256. (b) Bartlett, R. J. Annu. Rev. Phys. Chem. 1981, 32, 359. (c) Kuchanki, S. A,; Bartlett, R. J. Adv. Quantum Chem. 1986, 18, 281. (19) (a) Scuseria, G. E.; Scheiner, A. C.; Lee, T. J.; Rice, J. E.; Schaefer, H. F., 111. J . Chem. Phys. 1986,86, 2881. (b) Scuseria, G. E.; Janssen, C. L.; Schaefer, H. F., 111. J. Chem. Phys. 1988, 89, 7382. (20) (a) Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M. Chem. Phys. Lett. 1989, 157,479. (b) Scuseria, G. E.; Lee, T. J. J. Chem. Phys. 1990,93, 5851. (c) Scuseria, G. E. Chem. Phys. Lett. 1991,176, 27. (21) PSI 2.0, 1991, PSITECH, Inc., Watkinsville, GA. (22) Stanton, J. F.; Gauss, J.; Watts, J. D.; Lauderdale, W. J.; Bartlett, R. J. Int. J. Quantum Chem., Quantum Chem. Symp. 1992, 26, 879. (23) Huber, K. P.; Herzberg, G. Constants of Diatomic Molecules; Van Nostrand: Princeton, NJ, 1979. (24) Krassnova, K. S. Molecular Constants of Inorganic Substances; Khimia: Leningrad, Soviet Union, 1979 (in Russian). (25) Lofthus, A.; Krupenie, P. H. J. Phys. Chem. Ref. Data 1977,6,113. (26) Two sets of calculations have been performed to obtain an estimate of the 1s effect. In the first set no orbitals have been kept frozen (the results
ofthesecalculationsarereportedinTables1 and 2forN2andNO,respectively), while in the second set the 1s core orbitals and all virtual orbitals above 200 au have been kept frozen. (27) The numbers for N2 are somewhat different from the estimates reported recently by Bauschlicher and Partridge (BP) (Bauschlicher, C. W., Jr.; Partridge, H. J. Chem. Phys. 1994,100,4329), as BP‘s values a r e 4 0 0 2 A and +9 cm-1 for re and we, respectively. The reason for the discrepancy in we is that BP advocate a different strategy to measure the 1s effect: they do not separate the important effect caused by geometry change from those of changes in the treatment of the electronic problem. (28) The tendency of the CCSD(T) level of theory to result in too large re and quadratic force constant values at the same time can be used advantageously to calculate force fields and related molecular constants, such as frequencies, at the corresponding optimized theoretical geometry, as was demonstrated a number of times (see, for example, ref 3 and Lee, T. J.; Rice, J. E. J . Chem. Phys. 1991, 94, 1220).