TY - JOUR
T1 - Dynamic hyperpolarizability calculations of large systems
T2 - The linear-scaling divide-and-conquer approach
AU - Kobayashi, Masato
AU - Touma, Tsuguki
AU - Nakai, Hiromi
N1 - Funding Information:
Some of the present calculations were performed at the Research Center for Computational Science (RCCS), Okazaki Research Facilities, National Institutes of Natural Sciences (NINS). This study was supported in part by Grants-in-Aid for Challenging Exploratory Research “KAKENHI 22655008” and for Young Scientists (B) “KAKENHI 22750016” from the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan; by the Strategic Program for Innovative Research (SPIRE) of the MEXT; by the Global Center Of Excellence (COE) “Practical Chemical Wisdom” from the MEXT; by the Computational Materials Science Initiative (CMSI), Japan; and by a project research grant for “Practical in-silico chemistry for material design” from the Research Institute for Science and Engineering (RISE), Waseda University.
PY - 2012/2/28
Y1 - 2012/2/28
N2 - We report a linear-scaling computation method for evaluating the dynamic first hyperpolarizability based on the divide-and-conquer (DC) method. In the present scheme, we utilized the quasi-density-matrix expression derived from Wigners (2n 1) rule for , where the quasi-density matrices are constructed from the solution obtained via the DC time-dependent self-consistent field (TD-SCF) method [T. Touma, M. Kobayashi, and H. Nakai, Chem. Phys. Lett. 485, 247 (2010)10.1016/j.cplett.2009.12.043]. Numerical evaluation of -conjugated and saturated organic chain systems verified that the present scheme considerably reduces the computational time for the evaluation with a slight loss of accuracy, even around the singular frequency appearing at the electronic excitation energy. This evaluation indicates that the present linear-scaling TD-SCF scheme can also be used to estimate the molecular excitation energy. Furthermore, we succeeded in accurately evaluating the macroscopic second-harmonic generation coefficient of the polyvinylidene fluoride from the molecular (hyper)polarizabilities.
AB - We report a linear-scaling computation method for evaluating the dynamic first hyperpolarizability based on the divide-and-conquer (DC) method. In the present scheme, we utilized the quasi-density-matrix expression derived from Wigners (2n 1) rule for , where the quasi-density matrices are constructed from the solution obtained via the DC time-dependent self-consistent field (TD-SCF) method [T. Touma, M. Kobayashi, and H. Nakai, Chem. Phys. Lett. 485, 247 (2010)10.1016/j.cplett.2009.12.043]. Numerical evaluation of -conjugated and saturated organic chain systems verified that the present scheme considerably reduces the computational time for the evaluation with a slight loss of accuracy, even around the singular frequency appearing at the electronic excitation energy. This evaluation indicates that the present linear-scaling TD-SCF scheme can also be used to estimate the molecular excitation energy. Furthermore, we succeeded in accurately evaluating the macroscopic second-harmonic generation coefficient of the polyvinylidene fluoride from the molecular (hyper)polarizabilities.
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U2 - 10.1063/1.3687341
DO - 10.1063/1.3687341
M3 - Article
C2 - 22380033
AN - SCOPUS:84857848804
SN - 0021-9606
VL - 136
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 8
M1 - 084108
ER -