### Abstract

We present a method to calculate both on- and off-resonance vibrational Raman optical activities (VROAs) of molecules using time-dependent density functional theory. This is an extension of a method to calculate the normal VROA by including a finite lifetime of the electronic excited states in all calculated properties. The method is based on a short-time approximation to Raman scattering and is, in the off-resonance case, identical to the standard theory of Placzek. The normal and resonance VROA spectra are calculated from geometric derivatives of the different generalized polarizabilites obtained using linear response theory which includes a damping term to account for the finite lifetime. Gauge-origin independent results for normal VROA have been ensured using either the modified-velocity gauge or gauge-included atomic orbitals. For the resonance VROA only the modified-velocity gauge has been implemented. We present some initial results for H2 O2 and (S)-methyloxirane and compare with predictions from a simple two-state approximation.

Original language | English |
---|---|

Article number | 134101 |

Journal | Journal of Chemical Physics |

Volume | 127 |

Issue number | 13 |

DOIs | |

Publication status | Published - 2007 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

*Journal of Chemical Physics*,

*127*(13), [134101]. https://doi.org/10.1063/1.2768533

**Resonance vibrational Raman optical activity : A time-dependent density functional theory approach.** / Jensen, L.; Autschbach, J.; Krykunov, M.; Schatz, George C.

Research output: Contribution to journal › Article

*Journal of Chemical Physics*, vol. 127, no. 13, 134101. https://doi.org/10.1063/1.2768533

}

TY - JOUR

T1 - Resonance vibrational Raman optical activity

T2 - A time-dependent density functional theory approach

AU - Jensen, L.

AU - Autschbach, J.

AU - Krykunov, M.

AU - Schatz, George C

PY - 2007

Y1 - 2007

N2 - We present a method to calculate both on- and off-resonance vibrational Raman optical activities (VROAs) of molecules using time-dependent density functional theory. This is an extension of a method to calculate the normal VROA by including a finite lifetime of the electronic excited states in all calculated properties. The method is based on a short-time approximation to Raman scattering and is, in the off-resonance case, identical to the standard theory of Placzek. The normal and resonance VROA spectra are calculated from geometric derivatives of the different generalized polarizabilites obtained using linear response theory which includes a damping term to account for the finite lifetime. Gauge-origin independent results for normal VROA have been ensured using either the modified-velocity gauge or gauge-included atomic orbitals. For the resonance VROA only the modified-velocity gauge has been implemented. We present some initial results for H2 O2 and (S)-methyloxirane and compare with predictions from a simple two-state approximation.

AB - We present a method to calculate both on- and off-resonance vibrational Raman optical activities (VROAs) of molecules using time-dependent density functional theory. This is an extension of a method to calculate the normal VROA by including a finite lifetime of the electronic excited states in all calculated properties. The method is based on a short-time approximation to Raman scattering and is, in the off-resonance case, identical to the standard theory of Placzek. The normal and resonance VROA spectra are calculated from geometric derivatives of the different generalized polarizabilites obtained using linear response theory which includes a damping term to account for the finite lifetime. Gauge-origin independent results for normal VROA have been ensured using either the modified-velocity gauge or gauge-included atomic orbitals. For the resonance VROA only the modified-velocity gauge has been implemented. We present some initial results for H2 O2 and (S)-methyloxirane and compare with predictions from a simple two-state approximation.

UR - http://www.scopus.com/inward/record.url?scp=34948825487&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=34948825487&partnerID=8YFLogxK

U2 - 10.1063/1.2768533

DO - 10.1063/1.2768533

M3 - Article

AN - SCOPUS:34948825487

VL - 127

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 13

M1 - 134101

ER -