ORCID Profile
0000-0003-1011-6675
Current Organisation
University of Nottingham
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Publisher: American Chemical Society (ACS)
Date: 26-08-2008
DOI: 10.1021/JP801738F
Abstract: We present a simple algorithm, which we call the maximum overlap method (MOM), for finding excited-state solutions to self-consistent field (SCF) equations. Instead of using the aufbau principle, the algorithm maximizes the overlap between the occupied orbitals on successive SCF iterations. This prevents variational collapse to the ground state and guides the SCF process toward the nearest, rather than the lowest energy, solution. The resulting excited-state solutions can be treated in the same way as the ground-state solution and, in particular, derivatives of excited-state energies can be computed using ground-state code. We assess the performance of our method by applying it to a variety of excited-state problems including the calculation of excitation energies, charge-transfer states, and excited-state properties.
Publisher: Informa UK Limited
Date: 10-06-2002
Publisher: AIP Publishing
Date: 14-01-2003
DOI: 10.1063/1.1532311
Abstract: The computation of molecular Wigner intracules from Hartree–Fock wave functions using Gaussian basis functions is described. The Wigner intracule is a new type of intracule that contains information about both the relative position and momentum of the electrons. Two methods for evaluating the required integrals are presented. The first approach uses quadrature while the second requires summation of an infinite series.
Publisher: AIP Publishing
Date: 05-04-2004
DOI: 10.1063/1.1690233
Abstract: Intracules in position space, momentum space and phase space have been calculated for low-lying excited states of the He atom, Be atom, formaldehyde and butadiene. The phase-space intracules (Wigner intracules) provide significantly more information than the position- and momentum-space intracules, particularly for the Be atom. Exchange effects are investigated through the differences between corresponding singlet and triplet states.
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B511472A
Abstract: We present a radical approach to the calculation of electron correlation energies. Unlike conventional methods based on Hartree-Fock or density functional theory, it is based on the two-electron phase-space information in the Omega intracule, a three-dimensional function derived from the Wigner distribution. Our formula for the correlation energy is isomorphic to the Hartree-Fock energy expression but requires a new type of four-index integral. Preliminary results, obtained using a model that is based on the known correlation energies of small atoms, are encouraging.
Publisher: Royal Society of Chemistry (RSC)
Date: 2006
DOI: 10.1039/B517914A
Abstract: Advances in theory and algorithms for electronic structure calculations must be incorporated into program packages to enable them to become routinely used by the broader chemical community. This work reviews advances made over the past five years or so that constitute the major improvements contained in a new release of the Q-Chem quantum chemistry package, together with illustrative timings and applications. Specific developments discussed include fast methods for density functional theory calculations, linear scaling evaluation of energies, NMR chemical shifts and electric properties, fast auxiliary basis function methods for correlated energies and gradients, equation-of-motion coupled cluster methods for ground and excited states, geminal wavefunctions, embedding methods and techniques for exploring potential energy surfaces.
Publisher: Royal Society of Chemistry (RSC)
Date: 2020
DOI: 10.1039/C9CP06427C
Abstract: A strategy to create organic molecules with high degrees of radical spin multiplicity is reported in which molecular design is correlated with the behaviour of radical anions in a series of BODIPY dyads.
Publisher: AIP Publishing
Date: 25-03-2009
DOI: 10.1063/1.3092928
Abstract: The accuracy of core excitation energies and core electron binding energies computed within a Δself-consistent-field framework is assessed. The variational collapse of the core excited state is prevented by maintaining a singly occupied core orbital using an overlap criterion called the maximum overlap method. When applied to a wide range of small organic molecules, the resulting core excitation energies are not systematically underestimated as observed in time-dependent density functional theory and agree well with experiment. The accuracy of this approach for core excited states is illustrated by the calculation of the pre-edge features in x-ray absorption spectra of plastocyanin, which shows that accurate results can be achieved with Δself-consistent-field calculations when used in conjunction with uncontracted basis functions.
Publisher: American Chemical Society (ACS)
Date: 28-06-2013
DOI: 10.1021/JP404107J
Abstract: The calculation of the electronic circular dichroism (CD) spectra of the oxidized form of the blue copper proteins plastocyanin and cucumber basic protein and the relationship between the observed spectral features and the structure of the active site of the protein is investigated. Excitation energies and transition strengths are computed using multireference configuration interaction, and it is shown that computed spectra based on coordinates from the crystal structure or a single structure optimized in quantum mechanics/molecular mechanics (QM/MM) or ligand field molecular mechanics (LFMM) are qualitatively incorrect. In particular, the rotational strength of the ligand to metal charge transfer band is predicted to be too small or have the incorrect sign. By considering calculations on active site models with modified structures, it is shown that the intensity of this band is sensitive to the nonplanarity of the histidine and cysteine ligands coordinated to copper. Calculation of the ultraviolet absorption and CD spectra based upon averaging over many structures drawn from a LFMM molecular dynamics simulation are in good agreement with experiment, and superior to analogous calculations based upon structures from a classical molecular dynamics simulation. This provides evidence that the LFMM force field provides an accurate description of the molecular dynamics of these proteins.
Publisher: Wiley
Date: 2004
DOI: 10.1002/QUA.20125
Publisher: American Chemical Society (ACS)
Date: 21-11-2002
DOI: 10.1021/JA026099M
Abstract: A series of substituted benzoyl radicals has been generated by laser flash photolysis of alpha-hydroxy ketones, alpha-amino ketones, and acyl and bis(acyl)phosphine oxides, all of which are used commercially as photoinitiators in free radical polymerizations. The benzoyl radicals have been studied by fast time-resolved infrared spectroscopy. The absolute rate constants for their reaction with n-butylacrylate, thiophenol, bromotrichloromethane and oxygen were measured in acetonitrile solution. The rate constants of benzoyl radical addition to n-butylacrylate range from 1.3 x 10(5) to 5.5 x 10(5) M(-1) s(-1) and are about 2 orders of magnitude lower than for the n-butylacrylate addition to the counterradicals that are produced by alpha-cleavage of the investigated ketones. Density functional theoretical calculations have been performed in order to rationalize the observed reactivities of the initiating radicals. Calculations of the phosphorus-centered radicals generated by photolysis of an acyl and bis(acyl)phosphine oxide suggest that P atom Mulliken spin populations are an indicator of the relative reactivities of the phosphorus-centered radicals. The alpha-cleavage of (2,4,6-trimethylbenzoyl)phosphine oxide was studied by picosecond pump-probe and nanosecond step-scan time-resolved infrared spectroscopy. The results support a mechanism in which the alpha-cleavage occurs from the triplet excited state that has a lifetime less than or equal to the singlet excited state.
Location: United Kingdom of Great Britain and Northern Ireland
Location: United Kingdom of Great Britain and Northern Ireland
Location: United Kingdom of Great Britain and Northern Ireland
No related grants have been discovered for Nicholas Besley.