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

Abstract

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.

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

“…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.…”

Static and dynamic first hyperpolarizabilities from time‐dependent auxiliary density perturbation theory

“…Our calculated DFT SHG values were determined at the same wavelength as the experimental values. For CH 3 OH the VWN, PBE, and BP86 SHG values severely overestimate the CCSD result from90 and the experimental value from 92. This overestimation is considerably reduced by the mBP86 functional.…”

“…Because of their unreliability, we will not further discuss them. For CH 3 OH the VWN, PBE and BP86 hyperpolarizabilities severely overestimate the CCSD literature value 90. With the mBP86 functional a significant improvement is obtained.…”

Electronic and vibrational hyperpolarizabilities of alkali‐ and alkaline‐earth‐doped boron nitride nanotubes

“…The derivatives of the energy and components of μ, α, and β were calculated numerically, as described previously. [57,60] Equations (3)-(5) do not correctly describe the physical behavior of excited states once they have finite lifetimes. In consequence, the hyperpolarizabilities become infinite when they reach the excitation energy.…”

“…Since all derivatives of the μ components (which are nonzero by symmetry) have to be computed to calculate the term [ μα ] 0,0 , the additional effort to calculate the terms [ μ 3 ] 1,0 and [ μ 3 ] 0,1 is small. The derivatives of the energy and components of μ , α , and β were calculated numerically, as described previously …”