TY - JOUR
T1 - Approximate Quantum Dynamics using Ab Initio Classical Separable Potentials
T2 - Spectroscopic Applications
AU - Hirshberg, Barak
AU - Sagiv, Lior
AU - Gerber, R. Benny
N1 - Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/3/14
Y1 - 2017/3/14
N2 - Algorithms for quantum molecular dynamics simulations that directly use ab initio methods have many potential applications. In this article, the ab initio classical separable potentials (AICSP) method is proposed as the basis for approximate algorithms of this type. The AICSP method assumes separability of the total time-dependent wave function of the nuclei and employs mean-field potentials that govern the dynamics of each degree of freedom. In the proposed approach, the mean-field potentials are determined by classical ab initio molecular dynamics simulations. The nuclear wave function can thus be propagated in time using the effective potentials generated "on the fly". As a test of the method for realistic systems, calculations of the stationary anharmonic frequencies of hydrogen stretching modes were carried out for several polyatomic systems, including three amino acids and the guanine-cytosine pair of nucleobases. Good agreement with experiments was found. The method scales very favorably with the number of vibrational modes and should be applicable for very large molecules, e.g., peptides. The method should also be applicable for properties such as vibrational line widths and line shapes. Work in these directions is underway.
AB - Algorithms for quantum molecular dynamics simulations that directly use ab initio methods have many potential applications. In this article, the ab initio classical separable potentials (AICSP) method is proposed as the basis for approximate algorithms of this type. The AICSP method assumes separability of the total time-dependent wave function of the nuclei and employs mean-field potentials that govern the dynamics of each degree of freedom. In the proposed approach, the mean-field potentials are determined by classical ab initio molecular dynamics simulations. The nuclear wave function can thus be propagated in time using the effective potentials generated "on the fly". As a test of the method for realistic systems, calculations of the stationary anharmonic frequencies of hydrogen stretching modes were carried out for several polyatomic systems, including three amino acids and the guanine-cytosine pair of nucleobases. Good agreement with experiments was found. The method scales very favorably with the number of vibrational modes and should be applicable for very large molecules, e.g., peptides. The method should also be applicable for properties such as vibrational line widths and line shapes. Work in these directions is underway.
UR - http://www.scopus.com/inward/record.url?scp=85015224203&partnerID=8YFLogxK
U2 - 10.1021/acs.jctc.6b01129
DO - 10.1021/acs.jctc.6b01129
M3 - ???researchoutput.researchoutputtypes.contributiontojournal.article???
C2 - 28177631
AN - SCOPUS:85015224203
SN - 1549-9618
VL - 13
SP - 982
EP - 991
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 3
ER -