Linear response coupled cluster calculation of Raman scattering cross sections

The linear response coupled cluster singles and doubles (CCSD) method has been used to evaluate electric dipole polarizabilities, their geometric derivatives and Q-branch Raman scattering cross sections for five diatomic molecules: N2, CO, HF, HCl, and Cl2. A systematic study of basis set convergence has been carried out. Geometric derivatives of the frequency dispersion coefficients have been computed. This allowed to evaluate Raman intensities for arbitrary laser frequencies outside the resonance region. The geometric derivatives of polarizabilities, and therefore Raman intensities, exhibit stronger basis set dependence and dispersion effects than the polarizabilities themselves. Whereas the calculated polarizabilities are very close to experiment, the agreement of their geometric derivatives and of the Raman scattering cross sections with experiment is less excellent. We attribute this mainly to the limitations of Placzek’s theory (for Raman intensities) and to the low precision of the reference experi...

[1]  Jens Oddershede,et al.  Dynamic polarizabilities and raman intensities of CO, N2, HCl and Cl2 , 1982 .

[2]  Trygve Helgaker,et al.  The molecular structure of ferrocene , 1996 .

[3]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[4]  Hans-Joachim Werner,et al.  PNO-CI and PNO-CEPA studies of electron correlation effects , 1976 .

[5]  R. Bartlett,et al.  A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples , 1982 .

[6]  W. Holzer,et al.  Raman scattering of HF in the gas state and in liquid solution , 1974 .

[7]  J. Gauss,et al.  Polarizabilities of CO, N2, HF, Ne, BH, and CH+ from ab initio calculations: Systematic studies of electron correlation, basis set errors, and vibrational contributions , 1998 .

[8]  N. Bridge,et al.  The polarization of laser light scattered by gases , 1964, Proceedings of the Royal Society of London. Series A, Mathematical and physical sciences.

[9]  Benny G. Johnson,et al.  The prediction of Raman spectra by density functional theory. Preliminary findings , 1995 .

[10]  A. Stirling,et al.  Raman intensities from Kohn–Sham calculations , 1996 .

[11]  Trygve Helgaker,et al.  The integral‐direct coupled cluster singles and doubles model , 1996 .

[12]  P. Jørgensen,et al.  First-order one-electron properties in the integral-direct coupled cluster singles and doubles model , 1997 .

[13]  W. WashburnE.,et al.  International Critical Tables , 1927 .

[14]  G. Herzberg.  Molecular Spectra and Molecular Structure IV. Constants of Diatomic Molecules , 1939 .

[15]  J. G. Snijders,et al.  APPLICATION OF TIME-DEPENDENT DENSITY FUNCTIONAL RESPONSE THEORY TO RAMAN SCATTERING , 1996 .

[16]  G. Herzberg,et al.  Molecular Spectra and Molecular Structure , 1992 .

[17]  M. Mérawa,et al.  Theoretical determination of electric properties and Raman intensities of HCl and HF , 2000 .

[18]  Henrik Koch,et al.  Calculation of frequency-dependent polarizabilities using coupled-cluster response theory , 1994 .

[19]  R. Bartlett,et al.  Correlated calculations of molecular dynamic polarizabilities , 1997 .

[20]  J. Muenter.  Polarizability Anisotropy of Hydrogen Fluoride , 1972 .

[21]  B. Jursic.  Hybrid and gradient-corrected density functional theory computations of the cubane infrared and raman spectra , 1997 .

[22]  T. Spiro,et al.  Raman intensities and bond orders—A simplified delta function equation , 1977 .

[23]  Пётр Петрович Лазарев.  Handbuch der Radiologie , 1915 .

[24]  Alan K. Burnham,et al.  Measurement of the dispersion in polarizability anisotropies , 1975 .

[25]  Roger D. Amos,et al.  Raman intensities using time dependent density functional theory , 2000 .

[26]  R. Leeuwen,et al.  Exchange-correlation potential with correct asymptotic behavior. , 1994, Physical review. A, Atomic, molecular, and optical physics.

[27]  N. Ramsey,et al.  Stark hyperfine structure of hydrogen bromide , 1977 .

[28]  Trygve Helgaker,et al.  A direct atomic orbital driven implementation of the coupled cluster singles and doubles (CCSD) model , 1994 .

[29]  George Maroulis,et al.  A systematic study of basis set, electron correlation, and geometry effects on the electric multipole moments, polarizability, and hyperpolarizability of HCl , 1998 .

[30]  John F. Stanton,et al.  The effect of triple excitations in coupled cluster calculations of frequency-dependent polarizabilities , 1998 .

[31]  J. Gauss,et al.  Frequency-dependent polarizabilities and first hyperpolarizabilities of CO and H2O from coupled cluster calculations , 1999 .

[32]  Ove Christiansen,et al.  Cauchy moments and dispersion coefficients using coupled cluster linear response theory , 1997 .

[33]  Thom H. Dunning,et al.  Gaussian basis sets for use in correlated molecular calculations. V. Core-valence basis sets for boron through neon , 1995 .

[34]  William F. Murphy,et al.  Gas Phase Raman Intensities: A Review of “Pre-Laser” Data , 1969 .

[35]  T. Dunning,et al.  Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions , 1992 .

[36]  J. Oddershede,et al.  Ab initio calculation of the Raman intensity of the N2 molecule , 1979 .