+ Site Statistics
References:
54,258,434
Abstracts:
29,560,870
PMIDs:
28,072,757
+ Search Articles
+ Subscribe to Site Feeds
Most Shared
PDF Full Text
+ PDF Full Text
Request PDF Full Text
+ Follow Us
Follow on Facebook
Follow on Twitter
Follow on LinkedIn
+ Translate
+ Recently Requested

Stochastic Multiconfigurational Self-Consistent Field Theory



Stochastic Multiconfigurational Self-Consistent Field Theory



Journal of Chemical Theory and Computation 11(11): 5316-5325



The multiconfigurational self-consistent field theory is considered the standard starting point for almost all multireference approaches required for strongly correlated molecular problems. The limitation of the approach is generally given by the number of strongly correlated orbitals in the molecule, since its cost will grow exponentially with this number. We present a new multiconfigurational self-consistent field approach, wherein linear determinant coefficients of a multiconfigurational wave function are optimized via the stochastic full configuration interaction quantum Monte Carlo technique at greatly reduced computational cost, with nonlinear orbital rotation parameters updated variationally based on this sampled wave function. This extends this approach to strongly correlated systems with far larger active spaces than it is possible to treat via conventional means. By comparison with this traditional approach, we demonstrate that the introduction of stochastic noise in both the determinant amplitudes and the gradient and Hessian of the orbital rotations does not preclude robust and reliable convergence of the orbital optimization. It can even improve the ability to avoid convergence to local minima in the orbital space, and therefore aid in finding variationally lower-energy solutions. We consider the effect on the convergence of the orbitals as the number of walkers and the sampling time within the active space increases, as well as the effect on the final energy and error. The scope of the new protocol is demonstrated with a study of the increasingly strongly correlated electronic structure in a series of polycyclic aromatic hydrocarbons, up to the large coronene molecule in a complete active space of 24 π electrons in 24 orbitals, requiring only modest computational resources

(PDF emailed within 1 workday: $29.90)

Accession: 058906326

Download citation: RISBibTeXText

PMID: 26894240


Related references

Multiconfigurational self-consistent field theory with density matrix embedding: the localized active space self-consistent field method. Journal of Chemical Theory and Computation 2019, 2019

Study of singlet-triplet transitions in the ozone molecule using the multiconfigurational self-consistent field theory. High Energy Chemistry 40(4): 230-233, 2006

Can Multiconfigurational Self-Consistent Field Theory and Density Functional Theory Correctly Predict the Ground State of Metal-Metal-Bonded Complexes?. Journal of Chemical Theory and Computation 11(9): 4093-4101, 2015

Second-harmonic generation of solvated molecules using multiconfigurational self-consistent-field quadratic response theory and the polarizable continuum model. Journal of Chemical Physics 123(14): 144117-144117, 2005

Assessment of charge-transfer excitations with time-dependent, range-separated density functional theory based on long-range MP2 and multiconfigurational self-consistent field wave functions. Journal of Chemical Physics 139(18): 184308-184308, 2014

Self-consistent proteomic field theory of stochastic gene switches. Biophysical Journal 88(2): 828-850, 2004

The generalized active space concept in multiconfigurational self-consistent field methods. Journal of Chemical Physics 135(4): 044128-044128, 2011

Accurate ab initio density fitting for multiconfigurational self-consistent field methods. Journal of Chemical Physics 129(2): 024113-024113, 2008

Potential curves for inner-shell states of CO calculated at multiconfigurational self-consistent field level. Journal of Chemical Physics 134(2): 024107-024107, 2011

Multiconfigurational Self-Consistent Field Study of the Excited State Properties of 4-Thiouracil in the Gas Phase. Journal of Physical Chemistry A 108(35): 7241-7246, 2004

Investigation of 2P Be- shape resonances using a quadratically convergent complex multiconfigurational self-consistent field method. Journal of Physical Chemistry. B 112(50): 16214-9, 2009

Lattice-embedded multiconfigurational self-consistent-field calculations of the Mn-perturbed F-center defect in CaF2:Mn. Physical Review. B, Condensed Matter 52(1): 100-109, 1995

Evaluation of first- and second-order nonadiabatic coupling elements from large multiconfigurational self-consistent-field wave functions. Physical Review. A, General Physics 34(6): 4606-4614, 1986

Acceleration of self-consistent field convergence in ab initio molecular dynamics simulation with multiconfigurational wave function. Journal of Computational Chemistry 35(20): 1473-1480, 2014

Multiconfigurational Self-Consistent Field Calculations of the Magnetically Induced Current Density Using Gauge-Including Atomic Orbitals. Journal of Chemical Theory and Computation 9(5): 2189-2198, 2013