New Formulation and Implementation of Vibrational Self-Consistent Field Theory

Hansen M. B., Sparta M., Seidler P., Toffoli D., Christiansen O.

JOURNAL OF CHEMICAL THEORY AND COMPUTATION, cilt.6, sa.1, ss.235-248, 2010 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 6 Sayı: 1
  • Basım Tarihi: 2010
  • Doi Numarası: 10.1021/ct9004454
  • Dergi Adı: JOURNAL OF CHEMICAL THEORY AND COMPUTATION
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.235-248
  • Orta Doğu Teknik Üniversitesi Adresli: Hayır

Özet

A new implementation of the vibrational self-consistent field (VSCF) method is presented on the basis of a second quantization formulation. A so-called active terms algorithm is shown to be a significant improvement over a standard implementation reducing the computational effort by one order in the number of degrees of freedom. Various types of screening provide even further reductions in computational scaling and absolute CPU time. VSCF calculations on large polyaromatic hydrocarbon model systems are presented. Further, it is demonstrated that in cases where distant modes are not directly coupled in the Hamiltonian, down to linear scaling of the required CPU time with respect to the number of vibrational modes can be obtained. This is illustrated with calculations on simple model systems with up to 1 million degrees of freedom.