Force Constants and Dipole-Moment Derivatives of Molecules from Perturbed Hartree–Fock Calculations. I

Gerratt, Joseph; Mills, Ian

doi:10.1063/1.1670299

Cited by 630 publications

(240 citation statements)

References 27 publications

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“…(28). 91 These two updates of the matrix-vector product have thus to be computed consistently to the way the Coulomb and exchange contributions to the Fock matrix are calculated during the SCF procedure. In the actual case, this means that the former is obtained within the GPW scheme and the latter via 4-index ERIs.…”

Section: B the Analytic Derivatives For Ri-mp2mentioning

confidence: 99%

Forces and stress in second order Møller-Plesset perturbation theory for condensed phase systems within the resolution-of-identity Gaussian and plane waves approach

Ben

Hutter

VandeVondele

2015

The Journal of Chemical Physics

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The forces acting on the atoms as well as the stress tensor are crucial ingredients for calculating the structural and dynamical properties of systems in the condensed phase. Here, these derivatives of the total energy are evaluated for the second-order Møller-Plesset perturbation energy (MP2) in the framework of the resolution of identity Gaussian and plane waves method, in a way that is fully consistent with how the total energy is computed. This consistency is non-trivial, given the different ways employed to compute Coulomb, exchange, and canonical four center integrals, and allows, for example, for energy conserving dynamics in various ensembles. Based on this formalism, a massively parallel algorithm has been developed for finite and extended system. The designed parallel algorithm displays, with respect to the system size, cubic, quartic, and quintic requirements, respectively, for the memory, communication, and computation. All these requirements are reduced with an increasing number of processes, and the measured performance shows excellent parallel scalability and efficiency up to thousands of nodes. Additionally, the computationally more demanding quintic scaling steps can be accelerated by employing graphics processing units (GPU's) showing, for large systems, a gain of almost a factor two compared to the standard central processing unit-only case. In this way, the evaluation of the derivatives of the RI-MP2 energy can be performed within a few minutes for systems containing hundreds of atoms and thousands of basis functions. With good time to solution, the implementation thus opens the possibility to perform molecular dynamics (MD) simulations in various ensembles (microcanonical ensemble and isobaric-isothermal ensemble) at the MP2 level of theory. Geometry optimization, full cell relaxation, and energy conserving MD simulations have been performed for a variety of molecular crystals including NH3, CO2, formic acid, and benzene. The forces acting on the atoms as well as the stress tensor are crucial ingredients for calculating the structural and dynamical properties of systems in the condensed phase. Here, these derivatives of the total energy are evaluated for the second-order Møller-Plesset perturbation energy (MP2) in the framework of the resolution of identity Gaussian and plane waves method, in a way that is fully consistent with how the total energy is computed. This consistency is non-trivial, given the different ways employed to compute Coulomb, exchange, and canonical four center integrals, and allows, for example, for energy conserving dynamics in various ensembles. Based on this formalism, a massively parallel algorithm has been developed for finite and extended system. The designed parallel algorithm displays, with respect to the system size, cubic, quartic, and quintic requirements, respectively, for the memory, communication, and computation. All these requirements are reduced with an increasing number of processes, and the measured performance shows excellent parallel scala...

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Section: B the Analytic Derivatives For Ri-mp2mentioning

confidence: 99%

Forces and stress in second order Møller-Plesset perturbation theory for condensed phase systems within the resolution-of-identity Gaussian and plane waves approach

Ben

Hutter

VandeVondele

2015

The Journal of Chemical Physics

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“…As is the case for CPHF, 49 in CC theory their direct calculation is avoided by using the Dalgarno-Stewart interchange theorem, 50,51 and sometimes called the z-vector method for CPHF. 52,53 The governing equations of the FNOs are those expressed in Eqs.…”

Section: ͑17͒mentioning

confidence: 99%

Frozen natural orbital coupled-cluster theory: Forces and application to decomposition of nitroethane

Taube

Bartlett

2008

The Journal of Chemical Physics

112

128

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The frozen natural orbital ͑FNO͒ coupled-cluster method increases the speed of coupled-cluster ͑CC͒ calculations by an order of magnitude with no consequential error along a potential energy surface. This method allows the virtual space of a correlated calculation to be reduced by about half, significantly reducing the time spent performing the coupled-cluster ͑CC͒ calculation. This paper reports the derivation and implementation of analytical gradients for FNO-CC, including all orbital relaxation for both noncanonical and semicanonical perturbed orbitals. These derivatives introduce several new orbital relaxation contributions to the CC density matrices. FNO-CCSD͑T͒ and FNO-⌳CCSD͑T͒ are applied to a test set of equilibrium structures, verifying that these methods are capable of reproducing geometries and vibrational frequencies accurately, as well as energies. Several decomposition pathways of nitroethane are investigated using CCSD͑T͒ and ⌳CCSD͑T͒ with 60% of the FNO virtual orbitals in a cc-pVTZ basis, and find differences on the order of 5 kcal/ mol with reordering of the transition state energies when compared to B3LYP 6-311 +G͑3df ,2p͒.

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“…Molecules having higher values of dipole moment, molecular polarizability and first hyperpolarizability show more active NLO properties [36][37][38]. The total dipole moment, mean polarizability, anisotropy of polarizability and mean first order hyperpolarizability, using the x, y, z components are defined as µ = (µ…”

Section: Nlo Propertiesmentioning

confidence: 99%

Synthesis, Spectroscopic Investigation and Computational Studies of 2-Formyl-4-(Phenyldiazenyl)Phenyl Methyl Carbonate and 4-((4-Chlorophenyl)Diazenyl)-2-Formylphenyl Methyl Carbonate

Arokiasamy

Manikandan

Thanikachalam

et al. 2016

ILCPA

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ABSTRACT. Two new compounds namely 2-formyl-4-(phenyldiazenyl)phenyl methyl carbonate (FPMC) and 4-((4-chlorophenyl) diazenyl)-2-formylphenyl methyl carbonate (CFPMC) have been synthesized and have characterized using FT-IR, FT-Raman, 1 H and 13 C NMR techniques. Computational optimization studies have been carried out using Hatree-Fock (HF) and Density Functional Theory (DFT-B3LYP) methods with 6-31+G(d, p) basis set of Gaussian 09W software. The stable configuration of the title compounds were achieved theoretically by potential energy surface scan analysis. The complete vibrational assignments were performed on the basis of total energy distribution (TED) and natural bonding orbital (NBO) have been studied. Various parameters such as E HOMO , E LUMO , total energy, dipole moment, polarizability, first order hyperpolarizability, zero-point vibrational energy as well as thermal properties were analyzed and reported for the title compounds.

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Force Constants and Dipole-Moment Derivatives of Molecules from Perturbed Hartree–Fock Calculations. I

Cited by 630 publications

References 27 publications

Forces and stress in second order Møller-Plesset perturbation theory for condensed phase systems within the resolution-of-identity Gaussian and plane waves approach

Forces and stress in second order Møller-Plesset perturbation theory for condensed phase systems within the resolution-of-identity Gaussian and plane waves approach

Frozen natural orbital coupled-cluster theory: Forces and application to decomposition of nitroethane

Synthesis, Spectroscopic Investigation and Computational Studies of 2-Formyl-4-(Phenyldiazenyl)Phenyl Methyl Carbonate and 4-((4-Chlorophenyl)Diazenyl)-2-Formylphenyl Methyl Carbonate

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