Nonlinear response theory with relaxation : The first-order hyperpolarizability

• Based on the Ehrenfest theorem, an equation of motion that takes relaxation into account has been presented in wave-function theory, and the resulting response functions are nondivergent in the off-resonant as well as the resonant regions of optical frequencies. The derivation includes single- and multideterminant reference states. When applied to electric dipole properties, the response functions correspond to the phenomenological sum-over-states expressions of Orr and Ward [Mol. Phys. 20, 513 (1971)] for polarizabilities and hyperpolarizabilities of an isolated system. A universal dispersion formula is derived for the complex second-order response function. Response theory calculations are performed on lithium hydride and para-nitroaniline for off-resonant and resonant frequencies in the electro-optical Kerr effect and second-harmonic generation.

Ämnesord

NATURVETENSKAP  -- Kemi -- Teoretisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)

Nyckelord

Ehrenfest theorem

Hyperpolarizability

Nonlinear response theory

Sum-over-states

Optical Kerr effect

Polarization

Relaxation processes

Second harmonic generation

Theorem proving

Wave equations

Equations of motion

NATURAL SCIENCES

Publikations- och innehållstyp

ref (ämneskategori)

art (ämneskategori)