Yr Athro Peter Knowles
Professor of Theoretical Chemistry
- knowlespj@cardiff.ac.uk
- +44 (0)29 2087 9182
- Fax:
- +44 (0)29 2087 4030
- 55 Plas y Parc, Cathays, Caerdydd, CF10 3AT
- Sylwebydd y cyfryngau
Trosolwg
Links
Research Group: Theoretical and Computational Chemistry
Research Interests
- The development of new approximations and computational methods for improving the accuracy and reliability of first-principles molecular electronic structure.
- The implementation of ab initio methods for large molecules, including linear-scaling methodology, and hybrid embedding methods.
- High-performance computing, including parallel computing, and the development of interoperating chemistry components for the Grid.
For more information, click on the 'Research' tab above.
Teaching
Bywgraffiad
PhD, University of Cambridge (1984, N. C. Handy, Multiconfiguration self-consistent field theory). Research Fellow, St. Catharine$acirc; s College Cambridge (1983-9). Postdoctoral Research Fellow, University of Western Ontario (1985-6). SERC Advanced Research Fellow, University of Cambridge (1987-9). Lecturer in Chemistry, University of Sussex (1989-95). Professor of Theoretical Chemistry, University of Birmingham (1995-2004). Appointed as Professor of Theoretical Chemistry, Cardiff in 2004. RSC Harrison Memorial Prize (1988); RSC Marlow Medal (1994); RSC Industrially-sponsored Award in Computational Chemistry (2003).
Cyhoeddiadau
2021
- Knowles, P. J. 2021. The determination of point groups from imprecise molecular geometries. Journal of Mathematical Chemistry (10.1007/s10910-021-01302-x)
- Wang, Y., Knowles, P. J. and Wang, J. 2021. Information entropy as a measure of the correlation energy associated with the cumulant. Physical Review A 103(6), article number: 62808. (10.1103/PhysRevA.103.062808)
- Wang, Y.et al. 2021. Collins conjecture and information entropy in dissociating diatomic molecules. Physical Review A 103(4), article number: 42816. (10.1103/PhysRevA.103.042816)
2020
- Dresselhaus, T.et al. 2020. Coupling electrons and vibrations in molecular quantum chemistry. Journal of Chemical Physics 153(21), article number: 214114. (10.1063/5.0032900)
- Sibaev, M.et al. 2020. Molecular second-quantized Hamiltonian: electron correlation and non-adiabatic coupling treated on an equal footing. Journal of Chemical Physics 153(12), article number: 124102. (10.1063/5.0018930)
- Mordovina, U.et al. 2020. Polaritonic coupled-cluster theory. Physical Review Research 2(2), article number: 23262. (10.1103/PhysRevResearch.2.023262)
- Aïssaoui, L., Knowles, P. J. and Bouledroua, M. 2020. The role of spin-orbit effects in the mobility of N+ ions moving in a helium gas at low temperature. European Physical Journal D 74, article number: 155. (10.1140/epjd/e2020-10138-0)
- Werner, H.et al. 2020. The Molpro quantum chemistry package. Journal of Chemical Physics 152(14), article number: 144107. (10.1063/5.0005081)
- Kreplin, D. A., Knowles, P. J. and Werner, H. 2020. MCSCF optimization revisited. II. Combined first- and second-order orbital optimization for large molecules. Journal of Chemical Physics 152(7), article number: 74102. (10.1063/1.5142241)
2019
- Cooper, B.et al. 2019. Quantemol Electron Collisions (QEC): An enhanced expert system for performing electron molecule collision calculations using the R-matrix method. Atoms 7(4), article number: 97. (10.3390/atoms7040097)
- Polyak, I.et al. 2019. Ultrafast photoinduced dynamics of 1,3-Cyclohexadiene using XMS-CASPT2 surface hopping. Journal of Chemical Theory and Computation 15(7), pp. 3929-3940. (10.1021/acs.jctc.9b00396)
- Kreplin, D. A., Knowles, P. J. and Werner, H. 2019. Second-order MCSCF optimization revisited. I. Improved algorithms for fast and robust second-order CASSCF convergence. Journal of Chemical Physics 150(19), article number: 194106. (10.1063/1.5094644)
- Gritsenko, O. V., Wang, J. and Knowles, P. J. 2019. Symmetry dependence and universality of practical algebraic functionals in density-matrix-functional theory. Physical Review A 99(4), pp. -., article number: 42516. (10.1103/PhysRevA.99.042516)
- Polyak, I.et al. 2019. Direct quantum dynamics using variational Gaussian wavepackets and Gaussian process regression. Journal of Chemical Physics 150(4), pp. -., article number: 41101. (10.1063/1.5086358)
- Watson, N. A. I.et al. 2019. An extended computational study of Criegee intermediate - alcohol reactions. Journal of Physical Chemistry A 123(1), pp. 218-229. (10.1021/acs.jpca.8b09349)
2018
- Bacic, Z.et al. 2018. Precise characterisation of isolated molecules: general discussion. Faraday Discussions 212, pp. 137-155. (10.1039/C8FD90050G)
- Black, J. A. and Knowles, P. J. 2018. Statistical analysis of activation and reaction energies with quasi-variational coupled-cluster theory. Molecular Physics 116(11), pp. 1421-1427. (10.1080/00268976.2017.1400698)
- Black, J. A. and Knowles, P. J. 2018. Quasi-variational coupled-cluster theory: Performance of perturbative treatments of connected triple excitations. Journal of Chemical Physics 148(19), pp. -., article number: 194102. (10.1063/1.5006037)
- Wang, J. and Knowles, P. J. 2018. Reply to comment on 'Nonuniqueness of algebraic first-order density-matrix functionals'. Physical Review A 97(2), pp. -., article number: 26502. (10.1103/PhysRevA.97.026502)
2017
- Cooper, B.et al. 2017. Quantum chemistry in dataflow: Density-fitting MP2. Journal of Chemical Theory and Computation 13(11), pp. 5265-5272. (10.1021/acs.jctc.7b00649)
- Hirata, S.et al. 2017. One-particle many-body Green's function theory: Algebraic recursive definitions, linked-diagram theorem, irreducible-diagram theorem, and general-order algorithms. Journal of Chemical Physics 147(4), article number: 44108. (10.1063/1.4994837)
2016
- Beyer, A. N.et al. 2016. Quantum tunneling rates of gas-phase reactions from on-the-fly instanton calculations. Journal of Physical Chemistry Letters 7(21), pp. 4374-4379. (10.1021/acs.jpclett.6b02115)
2015
- Thomas, R. E.et al. 2015. Analytic nuclear forces and molecular properties from full configuration interaction quantum Monte Carlo. Journal of Chemical Physics 143(5), article number: 54108. (10.1063/1.4927594)
- Wang, J. and Knowles, P. J. 2015. Nonuniqueness of algebraic first-order density-matrix functionals. Physical review A 92(1), article number: 12520. (10.1103/PhysRevA.92.012520)
- Krylov, A. I.et al. 2015. What Is the price of open-source software?. The Journal of Physical Chemistry Letters 6(14), pp. 2751-2754. (10.1021/acs.jpclett.5b01258)
- Knowles, P. J. 2015. Compressive sampling in configuration interaction wavefunctions. Molecular Physics 113(13-14), pp. 1655-1660. (10.1080/00268976.2014.1003621)
- Clary, D. C., Knowles, P. J. and Tozer, D. J. 2015. Nicholas Charles Handy. 17 June 1941 — 2 October 2012. Biographical Memoirs of Fellows of the Royal Society, article number: rsbm20150002. (10.1098/rsbm.2015.0002)
2013
- Robinson, J. B. and Knowles, P. J. 2013. Rigorously extensive orbital-invariant renormalized perturbative triples corrections from quasi-variational coupled cluster theory. Journal of Chemical Physics 138(7), article number: 74104. (10.1063/1.4791636)
2012
- Knowles, P. J. and Robinson, J. B. 2012. Application of the quasi-variational coupled cluster method to the nonlinear optical properties of model hydrogen systems. The Journal of Chemical Physics 137(5), article number: 54301. (10.1063/1.4738758)
- Robinson, J. B. and Knowles, P. J. 2012. Quasi-variational coupled cluster theory. Journal of Chemical Physics 136(5), article number: 54114. (10.1063/1.3680560)
- Werner, H.et al. 2012. Molpro: a general-purpose quantum chemistry program package. Wiley Interdisciplinary Reviews: Computational Molecular Science 2(2), pp. 242-253. (10.1002/wcms.82)
- Robinson, J. B. and Knowles, P. J. 2012. Breaking multiple covalent bonds with Hartree-Fock-based quantum chemistry: quasi-variational coupled cluster theory with perturbative treatment of triple excitations. Physical Chemistry Chemical Physics 14(19), pp. 6729-6732. (10.1039/c2cp40698e)
- Robinson, J. B. and Knowles, P. J. 2012. Benchmark quasi-variational coupled cluster calculations of multiple bond breaking. Journal of Chemical Theory and Computation 8(8), pp. 2653-2660. (10.1021/ct300416b)
2011
- Robinson, J. B. and Knowles, P. J. 2011. Approximate variational coupled cluster theory. Journal of Chemical Physics 135(4), article number: 44113. (10.1063/1.3615060)
- Wang, M., May, A. J. and Knowles, P. J. 2011. Improved version of parallel programming interface for distributed data with multiple helper servers. Computer Physics Communications 182(7), pp. 1502-1506. (10.1016/j.cpc.2011.03.020)
2010
- Knowles, P. J. and Cooper, B. 2010. A linked electron pair functional. The Journal of Chemical Physics 133(22), article number: 224106. (10.1063/1.3507876)
- Cooper, B. and Knowles, P. J. 2010. Benchmark studies of variational, unitary and extended coupled cluster methods. The Journal of Chemical Physics 133(23), article number: 234102. (10.1063/1.3520564)
2009
- Knowles, P. J. and Cooper, B. 2009. Pair correlation functionals as approximations to variational coupled cluster. Abstracts of Papers of the American Chemical Society 238
- Wang, M., May, A. J. and Knowles, P. J. 2009. Parallel programming interface for distributed data. Computer Physics Communications 180(12), pp. 2673-2679. (10.1016/j.cpc.2009.05.002)
- Izsák, R.et al. 2009. High accuracy ab initio calculations on reactions of OH with 1-alkenes. The case of propene. Journal of Chemical Theory and Computation 5(9), pp. 2313-2321. (10.1021/ct900133v)
2004
- Celani, P.et al. 2004. The CIPT2 method: Coupling of multi-reference configuration interaction and multi-reference perturbation theory. Application to the chromium dimer. Molecular Physics 102(21-22), pp. 2369-2379. (10.1080/00268970412331317788)
- Polly, R.et al. 2004. Fast Hartree-Fock theory using local density fitting approximations. Molecular Physics 102(21-22), pp. 2311-2321. (10.1080/0026897042000274801)
- Diehr, M.et al. 2004. Theoretical rovibrational line intensities in the electronic ground state of ozone. Molecular Physics 102(21-22), pp. 2181-2189. (10.1080/00268970410001722993)
2003
- Werner, H., Manby, F. R. and Knowles, P. J. 2003. Fast linear scaling second-order Møller-Plesset perturbation theory (MP2) using local and density fitting approximations. The Journal of Chemical Physics 118(18), pp. 8149-8160. (10.1063/1.1564816)
- Polyansky, O. L.et al. 2003. High-Accuracy ab Initio Rotation-Vibration Transitions for Water. Science 299(5606), pp. 539-542. (10.1126/science.1079558)
2001
- Manby, F. R., Knowles, P. J. and Lloyd, A. W. 2001. The Poisson equation in density fitting for the Kohn-Sham Coulomb problem. Journal of chemical physics 115(20), pp. 9144-9148. (10.1063/1.1414370)
- Manby, F. R. and Knowles, P. J. 2001. Poisson equation in the Kohn-Sham Coulomb problem. Physical Review Letters 87(16), article number: 163001. (10.1103/PhysRevLett.87.163001)
Research Interests
- The development of new approximations and computational methods for improving the accuracy and reliability of first-principles molecular electronic structure.
- The implementation of ab initio methods for large molecules, including linear-scaling methodology, and hybrid embedding methods.
- High-performance computing, including parallel computing, and the development of interoperating chemistry components for the Grid.
Computation $acirc; whether from first principles or through simple models $acirc; has in recent years emerged as an equal partner of experiment in elucidating the structure, energetics and reactivity of materials. Our research efforts are focused on applying theory, through computation, to the prediction of the electronic structure of molecules, which determine molecular properties and the forces between atoms.
The key physical effect that presents a challenge for accurate representation is the correlated motion of electrons that is absent in the standard molecular-orbital picture of electronic structure. We are developing mathematical methods that support both the long-range correlation of electrons that is manifest when chemical bonds break, and the short-range correlated motion of two nearby electrons. A key aspect of such work is providing practical computer implementations that exploit available computational resources to the full, and that can be used by other researchers. Thus, much of the work of our group is directed towards the development of computer software. Challenges include computational methods that are applicable to large molecules, and the effective exploitation of high-performance parallel computers with thousands of processors. An important feature of this endeavour is the widespread distribution of our software package (Molpro) to the chemical community.
