NeON : An Atom AND a Molecule

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NeON: An Atom AND a Molecule Ryan C. Fortenberry, and Steven R. Gwaltney ACS Earth Space Chem., Just Accepted Manuscript • DOI: 10.1021/ acsearthspacechem.8b00019 • Publication Date (Web): 22 Mar 2018 Downloaded from http://pubs.acs.org on March 23, 2018

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ACS Earth and Space Chemistry

NeON+: An Atom AN D a Molecule Ryan C. Fortenberry∗,†,‡ and Steven R. Gwaltney¶ †Georgia Southern University, Department of Chemistry & Biochemistry, Statesboro, GA 30460, U.S.A. ‡Present Address: University of Mississippi, Department of Chemistry & Biochemistry, University, MS 38677 U.S.A. ¶Mississippi State University, Department of Chemistry, Mississippi State, MS 39762, U.S.A. E-mail: [email protected] Phone: 912-478-7694

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ACS Earth and Space Chemistry 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

Abstract The NeON+ molecule is stable with a Ne + NO+ dissociation energy of 0.90 kcal/mol. While this is small, the two vibrational modes that include the neon atom are less than this barrier at 57.9 cm−1 and 45.0 cm−1 . Hence, this “L”-shaped molecule will not readily vibrate itself apart in cold environments like the interstellar medium where the nitrosylium cation is believed to exist. While the 2359.2 cm−1 N≡O vibrational frequency is only slightly perturbed (but perturbed nonetheless) by the presence of the Ne atom, the other two fundamental vibrational frequencies will be observable in the THz region where future space telescopes may operate. Furthermore, the curiosity of a stable molecule whose constituent atomic symbols spell the name of one such atom give this structure a unique place in the chemical imagination. Hence, “neon” is both a molecule and an atom. Keywords: noble gas chemistry; astrochemistry; quantum chemistry; vibrational frequencies; THz spectroscopy

Graphical TOC Entry 10

Ne

N

8

7

Ne

O

N

20.183

15.9994

14.0067

O

2


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The periodic tables gracing the walls of most chemistry classrooms often serve as ciphers for coded messages instead of keys to unlocking the secrets of chemistry. Even so, chemists themselves seem to like a good turn-of-phrase, and the spelling of words through atomic symbols still crops up in chemical product advertising, internet science memes, and certainly undergraduate chemistry club T-shirts. Hence, we chemists never lose this desire to make words or phrases out of our beloved periodic table entries. However, creating an actual molecule that spells out an actual word is not easily undertaken since the rules of letter juxtaposition and chemical bonding could not be more different. While, “6-18-28-23-875” spells “CArNiVORe”, getting carbon, argon, nickel, vanadium, and oxygen somehow to coordinate to rhenium is likely chemically forbidden. Making a name of an atom is even more difficult. “77-8-7” does spell “IrON” even though iron (Fe) is not present in the molecule, but coordination of carbon monoxide to iridium is possible, in theory. Still, there may yet be at least a theoretically stable molecule whose atomic ingredients spell a constituent atom’s name: NeON+ . The greatest source of the common three letters “E”, “A”, or “R” in our periodic table cryptogram comes from the noble gas column. The noble gases are called such since they are sophomorically believed not to bond. However, noble gas chemistry has a rich modern history. 1 Xenon fluorides have been known for over half a century, 2 and hydrides like HArF has are experimentally stable at low temperatures. 3 Most excitingly, argonium (ArH+ ) has recently been detected in the interstellar medium (ISM), the first naturally-occurring noble gas molecule observed. 4–6 Consequently, recent work has produced bonding and spectroscopic analysis for fifteen more noble gas molecules 7–12 including, among others, the strongly bound 13 HeHHe+ proton-bound complex and the rotationally bright ArCN+ cation. 10 NeON+ is stable, just barely, but it should be present in interstellar environments of ∼ 400 K or less. Utilizing explicitly-correlated coupled cluster theory at the singles, doubles, and perturbative triples level, CCSD(T)-F12, 14,15 with the aug-cc-pVTZ basis set, 16–18 the equilibrium geometry is produced as depicted in Figure 1. The three highest occupied

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Figure 1: The equilibrium geometry of NeON+ .

Ne

O

N

molecular orbitals all correspond to the three degenerate p orbitals on the neon atom. There exists some overlap with the in-plane p from the neon and the in-plane π from the nitrosylium cation creating a tenuous bond. The CCSD(T)-F12/aug-cc-pVTZ Ne + NO+ → NeON+ bond energy (including harmonic zero-point vibrational energy corrections) is 0.90 kcal/mol or 314 cm−1 . Computations including basis set superposition error (BSSE) drop the bond energy to as little as 0.70 kcal/mol, but this structure will still be bound. Additionally, the molecule is non-linear in its lowest energy form. While a linear for of Ne−ON+ exists, its bond energy is only 0.03 kcal/mol and will likely not be bound with BSSE treatment. The Ne−NO+ isomer is not a minimum and reverts to one of the other isomers or dissociates. The lone pairs on the ends of the NO+ structure cannot engage in dative bonding with the full 2p Ne orbitals. Hence, the linear forms are unlikely to be observed. The most striking feature about Figure 1 is that the neon atom aligns itself along the p orbital axis of the nitrogen atom and not in the middle of the π cloud of the NO+ cation as has been observed in protonated acetylene. 19 The reason lies simply in the orbital nature of

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NO and NO+ itself. The double-occupation of a p orbital in oxygen, notably in NO radical, has been argued to exhibit anti-bonding-type character weakening any bonds that would normally reside on the oxygen atom. 20 Such behavior explains the exceptionally long O−O bond in the experimentally observed HOON molecule. 21,22 Figure 2: The CCSD(T)-F12/aug-cc-pVTZ PES scan of the Ne atom position with the black/purple area representing the lowest energy well. The blue dot represents the position of the N atom and red the O atom.

In the case of NeON+ , a CCSD(T)-F12/aug-cc-pVTZ scan of both the x and y positions of the neon atom relative to the fixed location of the NO+ moiety is shown in Figure 2. The origin is the midpoint between the nitrogen and the oxygen where the N−O bond length is 1.064 ˚ A. A delocalization of the minimum is present shown in Figure 2, but a nearly 90◦ 6

Ne−N−O for x =∼ 0.5 ˚ A is the most preferred position for the neon atom. The

dissociation barrier is computed to be 1.07 kcal/mol on this PES in line with that from the 5



full reaction described above and is applicable in all directions as shown in Figure 2. As the neon approaches the NO+ , the energies relative to the minimum surpass hundreds of kcal/mol very quickly once the neon atom is less than a radius of 3.5 ˚ A away from the origin. Again, this plot shows that NeON+ is bound and at least meta-stable in cold environments like the ISM where the ambient temperature is often below 80 K where the nitrogen monoxide radical is known 23 and the cation is speculated 24 to exist. In order to explore the possible presence of NeON+ (likely in space or under controlled laboratory conditions), the full vibrational frequencies and spectroscopic constants are provided in this work, as well. The CCSD(T)-based 14,25 CcCR quartic force field (QFF) methodology 26,27 is employed here with second-order vibrational perturbation theory (VPT2) and is defined in a later section. Table 1: The 1 1 A0 NeON+ CcCR QFF Force Constants (in mdyn/˚ An ·radm ).a F11 0.041128 F221 -0.0036 F1111 1.06 F3222 -0.19 F21 -0.008124 F222 202.3506 F2111 -0.03 F3311 0.74 F22 25.161072 F311 -0.1548 F2211 0.04 F3321 -0.08 F31 0.027886 F321 0.0098 F2221 0.03 F3322 -0.01 F32 0.007578 F322 -0.0153 F2222 1281.34 F3331 0.96 F33 0.031989 F331 -0.1681 F3111 0.65 F3332 -0.37 F111 -0.2307 F332 -0.0223 F3211 -0.11 F3333 1.56 F211 0.0129 F333 -0.2531 F3221 -0.04 a −8 1 mdyn = 10 N; n and m are exponents corresponding to the number of units from the type of modes present in the specific force constant. The force constants computed from the QFF are listed in Table 1. The F11 force constant corresponds to the Ne−O bond strength since the coordinates for this QFF are defined as the Ne−O bond, the N−O bond, and the 6 Ne−O−N bond angle, respectively. The interaction of the neon and oxygen atoms is therefore very weak while that of the nitrogen with the oxygen atom is incredibly strong in line with NO+ having the strongest known diatomic bond strength, greater even than N2 . While the bonding of the neon atom to NO+ is weak, the PES in Figure 2 is localized enough for a full quartic treatment to behave. While the vibrational averaging pushes the 6


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bond angle given in Table 2 to grow by nearly 5◦ , the bond length is still largely conserved compared with the equilibrium value. Regardless, this bond is quite long at ∼ 3.0 ˚ A indicating more van der Waals nature in the bond type. The fundamental vibrational frequencies have little intensity, but the dipole moment is fairly large. While the dipole moment here will vary largely with the position of the centerof-mass and, hence, the neon atom, this molecule will still have a strong rotational spectrum. Even though, NeON+ is non-linear, the molecule will exhibit near-prolate behavior due to the long-range interaction of the neon atom with the nitrosylium cation. An easy way to tell this complex apart from lone NO+ would be shifts in the vibrational frequency compared between the two species. However, CCSD(T)-F12/aug-cc-pVTZ harmonic vibrational frequencies differ by less than 0.5 cm−1 with that of the NeON+ cation lying to the blue. To corroborate such correlation, the CcCR QFF is known to produce vibrational frequencies to as good as 1 cm−1 compared with experiment. 19,28–31 Experiment 32 positions the vibrational frequency of free NO+ at 2360.5 cm−1 . The CcCR VPT2 frequency for NO+ is computed here to be 2358.6 cm−1 , a difference of 1.9 cm−1 . The ν1 CcCR value for the same mode in NeON+ is 2359.2 cm−1 indicating that a subsequent experimental value will likely fall at 2361.1 cm−1 or very close to it. Hence, the two species, NO+ and NeON+ , will exhibit nearly the same frequency in this range likely nullifying any distinction except for the most accurate of experimental procedures. However, the two frequencies are different enough that a the neon atom is affecting the N≡O stretch and may subsequently spread out the feature or cause a shoulder in resulting astronomical spectra. While the other vibrational frequencies are also relatively dim in intensity, they exist in a region of the spectrum typically believed to be populated by larger amplitude motions. The ν2 Ne−N stretch is 57.9 cm−1 , well below the dissociation energy, and displaying the brightest vibrational intensity. Hence, this level should be populated and potentially observed in the THz region making it a nice target for observation with emerging instruments such as NASA’s Cosmic Origins telescope currently under study to explore spectral features in this region

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of the electromagnetic spectrum. Additionally, such THz features will certainly distinguish NeON+ from the nitrosylium cation. Inclusion of the 22 Ne isotope shifts the ν2 frequency slightly and the rotational constants notably, but it has little effect on the other two vibrational frequencies as would be expected. However, the 0.1 cm−1 perturbation on the ν1 N≡O stretch further indicates that there is some influence, albeit small, of the neon atom with the NO+ moiety giving further evidence of some level of bonding between Ne and NO+ . In conclusion, NeON+ is a stable structure where even though the dissociation energy into Ne + NO+ is on the order of 1.0 kcal/mol, this molecule could exist at cold ISM temperatures and the Ne−N vibrational fundamental and even several overtones rest well below the point of dissociation. While the quirky composition of this molecule to utilize the atomic symbols and spell the name of the unique neon atom contained within the structure make NeON+ a curiosity, this molecule is actually applicable to astrochemistry especially in spectral analysis of the THz region making it worth exploring from both whimsical and practical perspectives.

Computational Details All coupled cluster computations make use of the MOLPRO 2015.1 quantum chemistry program. 33 The second-order Møller-Plesset perturbation theory (MP2), 6-31+G∗ basis set intensities and center-of-mass dipole moment are computed within the Gaussian09 program. 34–36 The CCSD(T)-F12/aug-cc-pVTZ PES scan is conducted from a set of coordinates with a dummy atom, X, at the origin, again, exactly midway between the fixed nitrogen and oxygen atoms. The Ne−X values are displaced by 0.1 ˚ A and stretch from 1.5 ˚ A to 7.0 ˚ A, and the Ne−X−O values are displaced by 1.0◦ from 0.0◦ to 180.0◦ creating a surface of roughly 10,000 points. These coordinates are transformed into Cartesian coordinates to produce Figure 2. The vibrational frequencies are determined initially from CCSD(T)/aug-cc-pV5Z geome-

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try optimizations 37,38 perturbed to include the difference in the geometrical parameters from CCSD(T) Martin-Taylor (MT) core correlating basis set 39 computations with and without core electrons. From this reference geometry, 129 points are generated from the three internal coordinates defined above. At each point, the CcCR energy is computed. It is defined from CCSD(T) computations producing the complete basis set (CBS) limit energy extrapolated from a aug-cc-pVTZ, QZ, and 5Z three-point formula 40 (“C”); core correlation (“cC”) computed from the difference of CCSD(T)/MT energies with the core electrons included and excluded; and Douglas-Kroll scalar relativity 41,42 (“R”). These energies define the QFF or fourth-order Taylor series approximation of the internuclear Hamiltonian defined as:

V =

1 X 1X 1X Fijk ∆i ∆j ∆k + Fijkl ∆i ∆j ∆k ∆l Fij ∆i ∆j + 2 ij 6 ijk 24 ijkl

(1)

with displacements of ∆i and force constants in terms of Fij... . The total CcCR energies are fit via a linear least-squares procedure generating a sum of squared residuals on the order of 1 × 10−17 a.u.2 This also provides the equilibrium geometry. Zeroing the gradients is done by refitting the QFF. The internal-coordinate quadratic, cubic, and quartic force constants (Table 1) are also generated in this step. VPT2 43,44 and secondorder rotational perturbation theory 45 are then run through the SPECTRO program. 46 A 2ν3 = ν2 type-1 Fermi resonance and a ν2 /ν3 C-type Coriolis resonance are also included in the VPT2 computations.

Acknowledgement The work undertaken by RCF is funded by NASA grant NNX17AH15G. Thanks are extended to Prof. T. Daniel Crawford of Virginia Tech for the use computing facilities employed as part of this work. The CheMVP program developed at the Center for Computational and Quantum Chemistry at the University of Georgia was utilized to produce Figure 1. GNUPLOT 4.6 was utilized to produce Figure 2. RCF would also like to thank Seth E. Keshel 9



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of Cypress Lake, TX for the fun had with his periodic table cryptograms in Mrs. Hood’s AP Physics class 2002-2003.

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(46) Gaw, J. F.; Willets, A.; Green, W. H.; Handy, N. C. In Advances in Molecular Vibrations and Collision Dynamics; Bowman, J. M., Ratner, M. A., Eds.; JAI Press, Inc.: Greenwich, Connecticut, 1991; pp 170–185.

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Table 2: The NeON+ and 22 NeON+ QFF Geometries, Spectroscopic Constants, and Vibrational Frequenciesa . 22 NeON+ NeON+ r0 (Ne−O) ˚ A 3.025 221 3.023 702 r0 (O−N) ˚ A 1.046 210 1.046 088 6 (Ne−O−N) 72.483 72.483 A0 cm−1 2.134589 2.133807 B0 cm−1 0.167406 0.158359 0.153467 0.145826 C0 cm−1 A1 cm−1 2.122426 2.121606 B1 cm−1 0.167094 0.158067 C1 cm−1 0.153131 0.145512 2.051270 2.048089 A2 cm−1 B2 cm−1 0.159272 0.150998 C2 cm−1 0.145605 0.138620 A3 cm−1 2.263017 2.264287 B3 cm−1 0.165772 0.156548 C3 cm−1 0.149079 0.141601 DJ kHz 99.128 89.437 DJK MHz 3.565 3.172 DK MHz 26.114 26.222 d1 kHz -10.096 -8.585 -2.306 -1.863 d2 kHz HJ Hz -7.432 -6.185 HJK Hz 578.553 479.681 HKJ kHz -42.993 -38.677 HK kHz 261.106 254.759 h1 Hz -1.099 -0.867 h2 Hz 0.404 0.296 h3 Hz 0.139 0.101 re (Ne−O) ˚ A 2.996 763 2.996 763 re (O−N) ˚ A 1.061 896 1.061 896 6 (Ne−O−N) 67.773 67.773 Ae cm−1 2.118115 2.117525 0.726058 0.163237 Be cm−1 Ce cm−1 0.159600 0.151554 µD 5.7 ω1 N−O stretch 2391.4 (1) 2391.4 ω2 Ne−N stretch 81.4 (13) 79.4 ω3 Bend 47.6 (3) 47.4 ν1 N−O stretch 2359.2 2359.3 ν2 Ne−N stretch 57.9 56.7 ν3 Bend 45.0 45.0 0-Pt 1254.5 1253.4 a Double harmonic MP2/6-31+G∗ intensities in parentheses.

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10

8

7

Ne

O

N

20.183

15.9994

14.0067


ACS Earth and Space Chemistry 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

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Ne

O

N ACS Paragon Plus Environment

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NeON : An Atom AND a Molecule

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