Treatment of nonlinear optical properties due to large amplitude anharmonic vibrational motions: Umbrella motion in NH3

Luis, Josep M.; Reis, Heribert; Παπαδόπουλος, Μάνθος Γ.

doi:10.1063/1.3171615

Cited by 38 publications

(31 citation statements)

References 60 publications

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“…Electron correlation effects were taken into account at the CCSD level through the coupled cluster linear, quadratic, and cubic response theories [38][39][40] implemented in the DALTON program. 41 In spite of the high level of the electron correlation treatment, the quality of the function basis set, and the careful computation of the vibrational corrections, a drawback of the methodology is that the normal coordinate approximation may not be an adequate model for large-amplitude modes, 13,14,16 as the modes related to the hydroxyl group. The discrepancy between the calculated vibrational frequency of the OH torsion mode ͑mode 1͒ and the experimental result, for instance, is an indication that the normal coordinate approximation is not reliable for this mode.…”

Section: Discussionmentioning

confidence: 99%

“…5,6 It has been shown that in many circumstances the corrections arising from the molecular vibrations are of similar magnitude, or even larger, than the electronic counterparts. [7][8][9][10][11][12][13][14][15][16] For systems on condensed phase the influence of the medium must also be considered, being the description of solvated systems usually made through simulation methods ͑molecular dynamics or Monte Carlo͒ or continuum models. [17][18][19][20][21][22][23] Methanol has been the subject of a number of recent theoretical and experimental investigations.…”

Section: Introductionmentioning

confidence: 99%

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Hyperpolarizabilities of the methanol molecule: A CCSD calculation including vibrational corrections

Dutra

Castro

Fonseca

et al. 2010

The Journal of Chemical Physics

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Basis set convergence of the coupled-cluster correction, MP2CCSD(T): Best practices for benchmarking noncovalent interactions and the attendant revision of the S22, NBC10, HBC6, and HSG databases J. Chem. Phys. 135, 194102 (2011) The electronic spectrum of the previously unknown HAsO transient molecule J. Chem. Phys. 135, 184308 (2011) Accurate ab initio ro-vibronic spectroscopy of the 2 CCN radical using explicitly correlated methods J. Chem. Phys. 135, 144309 (2011) Ab initio investigation of titanium hydroxide isomers and their cations, TiOH0, + and HTiO0, + J. Chem. Phys. 135, 144111 (2011) Additional information on J. Chem. Phys. In this work we present the results for hyperpolarizabilities of the methanol molecule including vibrational corrections and electron correlation effects at the CCSD level. Comparisons to random phase approximation results previously reported show that the electron correlation is in general important for both electronic contribution and vibrational corrections. The role played by the anharmonicities on the calculations of the vibrational corrections has also been analyzed and the obtained results indicate that the anharmonic terms are important for the dc-Pockels and dc-Kerr effects. For the other nonlinear optical properties studied the double-harmonic approximation is found to be suitable. Comparison to available experimental result in gas phase for the dc-second harmonic generation second hyperpolarizability shows a very good agreement with the electronic contribution calculated here while our total value is 14% larger than the experimental value.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Hyperpolarizabilities of the methanol molecule: A CCSD calculation including vibrational corrections

Dutra

Castro

Fonseca

et al. 2010

The Journal of Chemical Physics

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“…The importance of the nuclear motion contributions to various electromagnetic molecular properties is by now well understood. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] The zero-point vibrational corrections (ZPVCs) are proved to be non-negligible for the electron paramagnetic resonance (EPR), 18,20 nuclear magnetic resonance (NMR), 8,15,21 and non-linear optical (NLO) properties. 9,22 The so-called pure vibrational contributions to NLO properties 23 are often comparable or even larger in magnitude than that due to electronic motions.…”

Section: Introductionmentioning

confidence: 99%

“…9,22 The so-called pure vibrational contributions to NLO properties 23 are often comparable or even larger in magnitude than that due to electronic motions. 3,4,[9][10][11] Moreover, some of the experimentally observed effects, such as temperature dependence and isotope shifts of electric and magnetic properties, are entirely due to the effect of molecular vibrations and rotations. 15 Several successful methods for evaluating the rovibrational contributions to various molecular properties were formulated using the perturbation theory (PT) approach over the last few decades.…”

Section: Introductionmentioning

confidence: 99%

Ro-vibrational averaging of the isotropic hyperfine coupling constant for the methyl radical

Adam

Yachmenev

Yurchenko

et al. 2015

The Journal of Chemical Physics

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We present the first variational calculation of the isotropic hyperfine coupling constant of the carbon-13 atom in the CH3 radical for temperatures T = 0, 96, and 300 K. It is based on a newly calculated high level ab initio potential energy surface and hyperfine coupling constant surface of CH3 in the ground electronic state. The ro-vibrational energy levels, expectation values for the coupling constant, and its temperature dependence were calculated variationally by using the methods implemented in the computer program TROVE. Vibrational energies and vibrational and temperature effects for coupling constant are found to be in very good agreement with the available experimental data. We found, in agreement with previous studies, that the vibrational effects constitute about 44% of the constant's equilibrium value, originating mainly from the large amplitude out-of-plane bending motion and that the temperature effects play a minor role.

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“…Finally, a more rigorous study of the higher‐order vibrational properties would require the use of methods as employed for the NH 3 molecule in Ref. and will be the subject of a forthcoming study.…”

Section: Discussionmentioning

confidence: 99%

On the vibrational linear and nonlinear optical properties of compounds involving noble gas atoms: HXeOXeH, HXeOXeF, and FXeOXeF

et al. 2013

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The vibrational (hyper)polarizabilities of some selected Xe derivatives are studied in the context of Bishop-Kirtman perturbation theory (BKPT) and numerical finite field methodology. It was found that for this set of rare gas compounds, the static vibrational properties are quite large, in comparison to the corresponding electronic ones, especially those of the second hyperpolarizability. This also holds for the dc-Pockels β(-ω;ω,0), Kerr γ(-ω;ω,0,0) and electric field second harmonic generation γ (-2ω;ω,ω,0) effects, although the computed nuclear relaxation (nr) vibrational contributions are smaller in magnitude than the static ones. HXeOXeH was used to study the effects of electron correlation, basis set, and geometry. Geometry effects were found to lead to noticeable changes of the vibrational and electronic second hyperpolarizability. A limited study of the effect of Xe insertion to the nr vibrational properties is also reported. Assessment of the results revealed that Xe insertion has a remarkable effect on the nr (hyper)polarizabilities. In terms of the BKPT, this is associated with a remarkable increase of the electrical and mechanical anharmonicity terms. The latter is consistent with the anharmonic character of several vibrational modes reported for rare gas compounds.

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Treatment of nonlinear optical properties due to large amplitude anharmonic vibrational motions: Umbrella motion in NH3

Cited by 38 publications

References 60 publications

Hyperpolarizabilities of the methanol molecule: A CCSD calculation including vibrational corrections

Hyperpolarizabilities of the methanol molecule: A CCSD calculation including vibrational corrections

Ro-vibrational averaging of the isotropic hyperfine coupling constant for the methyl radical

On the vibrational linear and nonlinear optical properties of compounds involving noble gas atoms: HXeOXeH, HXeOXeF, and FXeOXeF

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