Isomerization of nitrosomethane to formaldoxime: energies, geometries, and frequencies from the parametric variational two-electron reduced-density-matrix method

The Journal of Chemical Physics
A Eugene DePrince, David A Mazziotti

Abstract

The isomerization of nitrosomethane to trans-formaldoxime is treated with the parametric variational two-electron reduced-density-matrix (2-RDM) method. In the parametric 2-RDM method, the ground-state energy is minimized with respect to a 2-RDM that is parameterized to be both size extensive and nearly N-representable. The calculations were performed with an efficient version of the 2-RDM method that we developed as an extension of the PSI3 ab initio package. Details of the implementation, which scales like configuration interaction with single and double excitations, are provided as well as a comparison of two optimization algorithms for minimizing the energy functional. The conversion of nitrosomethane to trans-formaldoxime can occur by one of two pathways: (i) a 1,3-sigmatropic hydrogen shift or (ii) two successive 1,2-sigmatropic hydrogen shifts. The parametric 2-RDM method predicts that the reaction channel involving two sequential 1,2-shifts is about 10 kcal/mol more favorable than the channel with a single 1,3-shift, which is consistent with calculations from other ab initio methods. We computed geometric parameters and harmonic frequencies for each stationary point on the reaction surfaces. Transition-state energies, g...Continue Reading

References

Feb 12, 1996·Physical Review Letters·H Nakatsuji, K Yasuda
Oct 2, 2001·The Journal of Organic Chemistry·J A LongK Lammertsma
Feb 28, 2002·Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics·David A Mazziotti
Mar 22, 2006·Accounts of Chemical Research·David A Mazziotti
Sep 1, 2006·The Journal of Chemical Physics·Eric CancèsMathieu Lewin
Oct 18, 2006·The Journal of Chemical Physics·Gergely Gidofalvi, David A Mazziotti
Jan 19, 2007·The Journal of Chemical Physics·Gergely Gidofalvi, David A Mazziotti
Apr 11, 2007·Journal of Computational Chemistry·T Daniel CrawfordWesley D Allen
Sep 18, 2007·The Journal of Chemical Physics·A Eugene DePrince, David A Mazziotti
May 2, 2009·The Journal of Chemical Physics·A Eugene DePrince, David A Mazziotti
May 20, 2009·The Journal of Chemical Physics·Loren Greenman, David A Mazziotti
Jan 9, 2010·The Journal of Physical Chemistry. a·Loren Greenman, David A Mazziotti
Jan 26, 2010·The Journal of Chemical Physics·A Eugene DePrince, David A Mazziotti

❮ Previous
Next ❯

Citations

Jan 3, 2013·The Journal of Chemical Physics·Christine A Schwerdtfeger, David A Mazziotti
Jul 27, 2012·The Journal of Chemical Physics·Christine A Schwerdtfeger, David A Mazziotti
Jun 15, 2011·The Journal of Chemical Physics·Liguo Kong, Edward F Valeev
Oct 30, 2014·International Journal of Molecular Sciences·Peter I Nagy
Oct 8, 2011·The Journal of Physical Chemistry. a·Christine A Schwerdtfeger, David A Mazziotti
Mar 21, 2013·The Journal of Physical Chemistry. a·Andrew J S Valentine, David A Mazziotti
Dec 8, 2020·Chemical Communications : Chem Comm·Santosh K SinghRalf I Kaiser

❮ Previous
Next ❯

Software Mentioned

CCSD
DETCI
GAMESS
GAUSSIAN
PSI3

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.