Linear and nonlinear susceptibilities from diffusion quantum Monte Carlo: Application to periodic hydrogen chains
We calculate the linear and nonlinear susceptibilities of periodic longitudinal chains of hydrogen dimers with different bond-length alternations using a diffusion quantum Monte Carlo approach. These quantities are derived from the changes in electronic polarization as a function of applied finite electric field-an approach we recently introduced and made possible by the use of a Berry-phase, many-body electric-enthalpy functional. Calculated susceptibilities and hypersusceptibilities are found to be in excellent agreement with the best estimates available from quantum chemistry-usually extrapolations to the infinite-chain limit of calculations for chains of finite length. It is found that while exchange effects dominate the proper description of the susceptibilities, second hypersusceptibilities are greatly affected by electronic correlations. We also assess how different approximations to the nodal surface of the many-body wave function affect the accuracy of the calculated susceptibilities.
Keywords: Berry phase ; bond lengths ; electric moments ; electron correlations ; exchange interactions (electron) ; hydrogen neutral molecules ; molecular ; moments ; Monte Carlo methods ; optical susceptibility ; polarisability ; wave functions ; 2nd hyperpolarizability ; molecular chains ; wave-functions ; polarization ; localization ; systems ; solids
Record created on 2012-06-29, modified on 2016-08-09