Professor Barry Carpenter
Professor Emeritus
- carpenterb1@cardiff.ac.uk
- +44(0) 29 2087 4000
- Room 1.46, Main Building, Park Place, Cardiff, CF10 3AT
Overview
Professor Carpenter's research interests are in the areas of theoretical and experimental investigations of reaction mechanisms, nonstatistical dynamics of reactive intermediates, photochemical reduction of CO2 and renewable sources of transportable fuels.
For more information, click on the 'Research' tab above.
Links
Research Group: Biological and Organic Chemistry
News Item: Towards an Artificial Leaf
Biography
PhD University College London (1973, H. M. R. Hoffmann, Organic Chemistry). NATO Postdoctoral Fellow, Yale University (1973-75, J. A. Berson). Assistant, Associate, and Full Professor of Chemistry, Cornell University (1975-2004). Department Chair, Department of Chemistry and Chemical Biology, Cornell University (2001-4). Horace White Professor, Cornell University (2004-6). Director of the Physical Organic Chemistry Centre.
Publications
2019
- Hare, S. R.et al. 2019. Low dimensional representations along intrinsic reaction coordinates and molecular dynamics trajectories using interatomic distance matrices. Chemical Science 10(43), pp. 9954-9968. (10.1039/C9SC02742D)
- Garcia-Mesguer, R., Carpenter, B. and Wiggins, S. 2019. The influence of the solvent's mass on the location of the dividing surface for a model Hamiltonian. Chemical Physics Letters: X, article number: 100030. (10.1016/j.cpletx.2019.100030)
- Garcia-Meseguer, R. and Carpenter, B. K. 2019. Re-evaluating the transition state for reactions in solution. European Journal of Organic Chemistry 2019(2-3), pp. 254-266. (10.1002/ejoc.201800841)
2018
- Rapf, R. J.et al. 2018. Environmental processing of lipids driven by aqueous photochemistry of α-Keto acids. ACS Central Science 4(5), pp. 624-630. (10.1021/acscentsci.8b00124)
- Carpenter, B. K.et al. 2018. Dynamics on the double morse potential: a paradigm for roaming reactions with no saddle points. Regular and Chaotic Dynamics 23(1), pp. 60-79. (10.1134/S1560354718010069)
2017
- Vaida, V.et al. 2017. Comment on “reactivity of ketyl and acetyl radicals from direct solar actinic photolysis of aqueous pyruvic acid”. Journal of Physical Chemistry A 121(45), pp. 8738-8740. (10.1021/acs.jpca.7b06018)
- Carpenter, B. K.et al. 2017. Empirical classification of trajectory data: An opportunity for the use of machine learning in molecular dynamics. Journal of Physical Chemistry B 122(13), pp. 3230. (10.1021/acs.jpcb.7b08707)
- Rapf, R. J.et al. 2017. Mechanistic description of photochemical oligomer formation from aqueous pyruvic acid. Journal of Physical Chemistry A 121(22), pp. 4272-4282. (10.1021/acs.jpca.7b03310)
- Rapf, R. J.et al. 2017. Photochemical synthesis of oligomeric amphiphiles from alkyl oxoacids in aqueous environments. Journal of the American Chemical Society 139(20), pp. 6946-6959. (10.1021/jacs.7b01707)
- Mauguière, F. A.et al. 2017. Roaming: a phase space perspective. Annual Review of Physical Chemistry 68(1), pp. 499-524. (10.1146/annurev-physchem-052516-050613)
2016
- Perkins, R. J.et al. 2016. Chemical equilibria and kinetics in aqueous solutions of zymonic acid. Journal of Physical Chemistry A 120(51), pp. 10096-10107. (10.1021/acs.jpca.6b10526)
- Reed Harris, A. E.et al. 2016. Gas-phase photolysis of pyruvic acid: the effect of pressure on reaction rates and products. Journal of Physical Chemistry A 120(51), pp. 10123-10133. (10.1021/acs.jpca.6b09058)
- Carpenter, B. K., Harvey, J. N. and Orr-Ewing, A. J. 2016. The study of reactive intermediates in condensed phases. Journal of the American Chemical Society 138(14), pp. 4695-4705. (10.1021/jacs.6b01761)
- Mauguière, F. A. L.et al. 2016. Toward understanding the roaming mechanism in H + MgH → Mg + HH reaction. Journal of Physical Chemistry A 120(27), pp. 5145-5154. (10.1021/acs.jpca.6b00682)
- Mauguière, F. A. L.et al. 2016. Phase space barriers and dividing surfaces in the absence of critical points of the potential energy: Application to roaming in ozone. Journal of Chemical Physics 144(5), article number: 54107. (10.1063/1.4940798)
2015
- Carpenter, B. K. 2015. Beauty in simplicity: celebrating 50 years of the Woodward-Hoffmann rules. The Journal of Organic Chemistry 80(23), pp. 11630. (10.1021/acs.joc.5b02469)
- Mauguiere, F. A. L.et al. 2015. Phase space structures explain hydrogen atom roaming in formaldehyde decomposition. Journal of Physical Chemistry Letters 6(20), pp. 4123-4128. (10.1021/acs.jpclett.5b01930)
- Kramer, Z. C.et al. 2015. A reaction path bifurcation in an electrocyclic reaction: the ring-opening of the cyclopropyl radical. Journal of Physical Chemistry A 119(25), pp. 6611-6630., article number: 150603223723008. (10.1021/acs.jpca.5b02834)
- Carpenter, B. K., Harvey, J. N. and Glowacki, D. R. 2015. Prediction of enhanced solvent-induced enantioselectivity for a ring opening with a bifurcating reaction path. Physical Chemistry Chemical Physics 17(13), pp. 8372-8381. (10.1039/C4CP05078A)
2014
- Carpenter, B. K. 2014. Effect of a chiral electrostatic cavity on product selection in a reaction with a bifurcating reaction path. Theoretical Chemistry Accounts 133(8), article number: 1525. (10.1007/s00214-014-1525-2)
- Collins, P.et al. 2014. Nonstatistical dynamics on the caldera. Journal of Chemical Physics 141(3), article number: 34111. (10.1063/1.4889780)
- Griffith, E. C.et al. 2014. Photoinitiated synthesis of self-assembled vesicles. Journal of the American Chemical Society 136(10), pp. 3784-3787. (10.1021/ja5006256)
2013
- Griffith, E. C.et al. 2013. Photochemistry of aqueous pyruvic acid. Proceedings of the National Academy of Sciences 110(29), pp. 11714-11719. (10.1073/pnas.1303206110)
- Carpenter, B. K. 2013. Energy disposition in reactive intermediates. Chemical Reviews, article number: 130301085532008. (10.1021/cr300511u)
- Collins, P.et al. 2013. Nonstatistical dynamics on potentials exhibiting reaction path bifurcations and valley-ridge inflection points. Journal of Chemical Physics 139(15), article number: 154108. (10.1063/1.4825155)
2011
- Goldman, L. M., Glowacki, D. R. and Carpenter, B. K. 2011. Nonstatistical dynamics in unlikely places: [1,5] hydrogen migration in chemically activated cyclopentadiene. Journal of the American Chemical Society 133(14), pp. 5312-5318. (10.1021/ja1095717)
- Richardson, R. D., Holland, E. J. and Carpenter, B. K. 2011. A renewable amine for photochemical reduction of CO2. Nature Chemistry 3(4), pp. 301-303. (10.1038/nchem.1000)
- Carpenter, B. K. 2011. Taking the High Road and Getting There Before You. Science 332(6035), pp. 1269-1270. (10.1126/science.1206693)
- Rehbein, J. and Carpenter, B. K. 2011. Do we fully understand what controls chemical selectivity?. Physical Chemistry Chemical Physics 13(47), pp. 20906-20922. (10.1039/c1cp22565k)
2010
- Carpenter, B. K. 2010. Kinetic isotope effects: Unearthing the unconventional. Nature Chemistry 2(2), pp. 80-82. (10.1038/nchem.531)
2009
- Carpenter, B. K., Pittner, J. and Veis, L. 2009. Ab Initio Calculations on the Formation and Rearrangement of Spiropentane. Journal of Physical Chemistry A 113(39), pp. 10557-10563. (10.1021/jp905368b)
- Carpenter, B. K. 2009. The transition-state theory description of enzyme catalysis for classically activated reactions. In: Allemann, R. K. and Scrutton, N. S. eds. Quantum tunnelling in enzyme-catalysed reactions. London: RSC Publishing, pp. 1-17., (10.1039/9781847559975-00001)
2008
- Litovitz, A. E., Keresztes, I. and Carpenter, B. K. 2008. Evidence for nonstatistical dynamics in the Wolff rearrangement of a carbene. Journal of the American Chemical Society 130(36), pp. 12085-12094. (10.1021/ja803230a)
- Richardson, R. D. and Carpenter, B. K. 2008. A computational study of remote C-H activation by amine radical cations: implications for the photochemical reduction of carbon dioxide. Journal of the American Chemical Society 130(10), pp. 3169-3180. (10.1021/ja710595u)
- Richardson, R. D. and Carpenter, B. K. 2008. A Computational Study of Remote C-H Activation by Amine Radical Cations: Implications for the Photochemical Reduction of Carbon Dioxide. Journal of the American Chemical Society 130(10), pp. 3169-3180. (10.1021/ja710595u)
2007
- Carpenter, B. K. 2007. Computational study of CO2 reduction by amines. Journal of Physical Chemistry A 111(19), pp. 3719-3726. (10.1021/jp0660076)
2005
- Cremeens, M. E., Hughes, T. S. and Carpenter, B. K. 2005. Mechanistic studies on the cyclization of (Z)-1,2,4-heptatrien-6-yne in methanol: a possible nonadiabatic thermal reaction. Journal of the American Chemical Society 127(18), pp. 6652-6661. (10.1021/ja0445443)
2002
- Nummela, J. A. and Carpenter, B. K. 2002. Nonstatistical Dynamics in Deep Potential Wells: A Quasiclassical Trajectory Study of Methyl Loss from the Acetone Radical Cation. Journal of the American Chemical Society 124(29), pp. 8512-8513. (10.1021/ja026230q)
- Reyes, M. B., Lobkovsky, E. B. and Carpenter, B. K. 2002. Interplay of Orbital Symmetry and Nonstatistical Dynamics in the Thermal Rearrangements of Bicyclo[n.1.0]polyenes. Journal of the American Chemical Society 124(4), pp. 641-651. (10.1021/ja017083j)
- Theoretical and experimental investigations of reaction mechanisms.
- Nonstatistical dynamics of reactive intermediates.
- Photochemical reduction of CO2.
- Renewable sources of transportable fuels.
For most of the history of studies in organic reaction mechanisms, transient intermediates, which play crucial roles in a wide variety of reactions, have been presumed to behave in ways that are adequately described by traditional kinetic models, such as Transition State Theory. However, in recent years it has become apparent that reactive intermediates may exhibit effects that are traceable to breakdowns in some of the key approximations in the standard kinetic models. The symptoms of these effects are that product ratios may not reflect the apparent symmetries of the intermediates from which they are formed, the intermediates may have no well-defined lifetimes, and intermediates may even form products in an oscillatory manner. The origins and scope of these effects constitute one of the principal areas of research in the Carpenter group. The work involves a combination of organic synthesis, kinetics, molecular dynamics simulation, and ultrafast spectroscopy.
The Carpenter group has also had a longstanding interest in the mechanistic organic chemistry associated with energy. While at Cornell, this research was centred on hydrocarbon combustion, but at Cardiff the group has shifted its focus to address issues of renewable energy. Of particular interest is the question of how one can use renewable sources of energy, such as sunlight, to produce transportable fuels. This work, like the more fundamental research on reactive intermediates, involves a tight coupling of theoretical and experimental investigations.