- Letter
- Open Access
Chiral photoelectron spectroscopy using unpolarized light
Phys. Rev. A 109, L060802 – Published 17 June, 2024
DOI: https://doi.org/10.1103/PhysRevA.109.L060802
Abstract
This Letter studies the symmetry properties of general vector correlations resulting from one-photon excitation of chiral molecules. We show that the parity-odd second rank tensor is nonzero for molecules in all chiral point groups , and . This chirality-sensitive tensor is nonzero even for chiral isotopomers excited by linearly polarized or even unpolarized light. We develop an irreducible tensor theory based on Curie's limiting groups. As an example of vector correlations, recoil-frame photoelectron angular distributions (RFPADs) are calculated for methyloxirane and . The difference in the RFPAD between a chiral molecule and its mirror image reaches % of the maximum value for the RFPAD for unpolarized light and % of the value for linearly polarized light. Chiral sensitivity in vector correlation is a quite general phenomenon arising from one-photon excitation by unpolarized and linearly polarized light, and we expect it to be of great importance in time-resolved spectroscopy of ultrafast chemical reactions.
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References (85)
- B. Ritchie, Theory of the angular distribution of photoelectrons ejected from optically active molecules and molecular negative ions, Phys. Rev. A 13, 1411 (1976).
- N. A. Cherepkov, Circular dichroism of molecules in the continuous absorption region, Chem. Phys. Lett. 87, 344 (1982).
- N. Böwering, T. Lischke, B. Schmidtke, N. Müller, T. Khalil, and U. Heinzmann, Asymmetry in photoelectron emission from chiral molecules induced by circularly polarized light, Phys. Rev. Lett. 86, 1187 (2001).
- S.-Y. Liu, K. Alnama, J. Matsumoto, K. Nishizawa, H. Kohguchi, Y.-P. Lee, and T. Suzuki, He I ultraviolet photoelectron spectroscopy of benzene and pyridine in supersonic molecular beams using photoelectron imaging, J. Phys. Chem. A 115, 2953 (2011).
- A. V. Golovin, N. A. Cherepkov, and V. V. Kuznetsov, Photoionization of oriented molecules in a gas phase, Z. Phys. D 24, 371 (1992).
- P. Downie and I. Powis, Molecule-frame photoelectron angular distributions from oriented molecules, Phys. Rev. Lett. 82, 2864 (1999).
- O. Kfir, P. Grychtol, E. Turgut, R. Knut, D. Zusin, D. Popmintchev, T. Popmintchev, H. Nembach, J. M. Shaw, A. Fleischer, H. Kapteyn, M. Murnane, and O. Cohen, Generation of bright phase-matched circularly-polarized extreme ultraviolet high harmonics, Nat. Photonics 9, 99 (2015).
- T. Kaneyasu, Y. Hikosaka, M. Fujimoto, H. Iwayama, and M. Katoh, Controlling the orbital alignment in atoms using cross-circularly polarized extreme ultraviolet wave packets, Phys. Rev. Lett. 123, 233401 (2019).
- J. C. Hansen and R. S. Berry, Angular distributions of electrons from resonant two-photon ionization of molecules, J. Chem. Phys. 80, 4078 (1984).
- A. G. Harvey, Z. Mašín, and O. Smirnova, General theory of photoexcitation induced photoelectron circular dichroism, J. Chem. Phys. 149, 064104 (2018).
- R. Uberna, R. D. Hinchliffe, and J. I. Cline, Photofragment correlation measured by resonance-enhanced multiphoton ionization: Selective probing of bipolar moments and detection of chiral dynamics, J. Chem. Phys. 103, 7934 (1995).
- A. Busalla, K. Blum, and D. G. Thompson, Collisions with chiral molecules prepared by optical pumping, J. Phys. B 33, 2317 (2000).
- D. Patterson and J. M. Doyle, Sensitive chiral analysis via microwave three-wave mixing, Phys. Rev. Lett. 111, 023008 (2013).
- A. Yachmenev and S. N. Yurchenko, Detecting chirality in molecules by linearly polarized laser fields, Phys. Rev. Lett. 117, 033001 (2016).
- M. Nakamura, F. Palazzetti, P.-Y. Tsai, S.-J. Yang, K.-C. Lin, T. Kasai, D.-C. Che, A. Lombardi, and V. Aquilanti, Vectorial imaging of the photodissociation of 2-bromobutane oriented via hexapolar state selection, Phys. Chem. Chem. Phys. 21, 14164 (2019).
- X. B. Planas, A. Ordóñez, M. Lewenstein, and A. S. Maxwell, Ultrafast imaging of molecular chirality with photoelectron vortices, Phys. Rev. Lett. 129, 233201 (2022).
- N. Cherepkov, Polarization and orientation phenomena in photoionization of molecules, Adv. At. Mol. Opt. Phys. 34, 207 (1994).
- N. A. Cherepkov and V. V. Kuznetsov, Photoionization of oriented molecules, Z. Phys. D 7, 271 (1987).
- U. Heinzmann and N. A. Cherepkov, Spin polarization in photoionization, in VUV and Soft X-Ray Photoionization, edited by U. Becker and D. A. Shirley (Springer, New York, 1996), pp. 521–559.
- H. Kagan, A. Moradpour, J. F. Nicoud, G. Balavoine, and G. Tsoucaris, Photochemistry with circularly polarized light. Synthesis of optically active hexahelicene, J. Am. Chem. Soc. 93, 2353 (1971).
- S. Mayer and J. Kessler, Experimental verification of electron optic dichroism, Phys. Rev. Lett. 74, 4803 (1995).
- A. Owens, A. Yachmenev, S. N. Yurchenko, and J. Küpper, Climbing the rotational ladder to chirality, Phys. Rev. Lett. 121, 193201 (2018).
- M. Leibscher, E. Pozzoli, A. Blech, M. Sigalotti, U. Boscain, and C. P. Koch, Quantum control of rovibrational dynamics and application to light-induced molecular chirality, Phys. Rev. A 109, 012810 (2024).
- A. Buckingham, Chirality in NMR spectroscopy, Chem. Phys. Lett. 398, 1 (2004).
- E. Hirota, Triple resonance for a three-level system of a chiral molecule, Proc. Jpn. Acad. Ser. 88, 120 (2012).
- D. Patterson, M. Schnell, and J. M. Doyle, Enantiomer-specific detection of chiral molecules via microwave spectroscopy, Nature (London) 497, 475 (2013).
- M. Leibscher, T. F. Giesen, and C. P. Koch, Principles of enantio-selective excitation in three-wave mixing spectroscopy of chiral molecules, J. Chem. Phys. 151, 014302 (2019).
- V. Marichez, A. Tassoni, R. P. Cameron, S. M. Barnett, R. Eichhorn, C. Genet, and T. M. Hermans, Mechanical chiral resolution, Soft Matter 15, 4593 (2019).
- A. F. Ordonez and O. Smirnova, Generalized perspective on chiral measurements without magnetic interactions, Phys. Rev. A 98, 063428 (2018).
- R. L. Dubs, S. N. Dixit, and V. McKoy, Circular dichroism in photoelectron angular distributions from oriented linear molecules, Phys. Rev. Lett. 54, 1249 (1985).
- J. Berakdar and H. Klar, Circular dichroism in double photoionization, Phys. Rev. Lett. 69, 1175 (1992).
- T. Jahnke et al., Circular dichroism in K-shell ionization from fixed-in-space CO and molecules, Phys. Rev. Lett. 88, 073002 (2002).
- M. Tia et al., Observation of enhanced chiral asymmetries in the inner-shell photoionization of uniaxially oriented methyloxirane enantiomers, J. Phys. Chem. Lett. 8, 2780 (2017).
- R. N. Dixon, The determination of the vector correlation between photofragment rotational and translational motions from the analysis of Doppler-broadened spectral line profiles, J. Chem. Phys. 85, 1866 (1986).
- J. Berakdar and H. Klar, Chiral multi-electron emission, Phys. Rep. 340, 473 (2001).
- P. Herwig, K. Zawatzky, M. Grieser, O. Heber, B. Jordon-Thaden, C. Krantz, O. Novotný, R. Repnow, V. Schurig, D. Schwalm, Z. Vager, A. Wolf, O. Trapp, and H. Kreckel, Imaging the absolute configuration of a chiral epoxide in the gas phase, Science 342, 1084 (2013).
- M. Pitzer, M. Kunitski, A. S. Johnson, T. Jahnke, H. Sann, F. Sturm, L. P. H. Schmidt, H. Schmidt-Böcking, R. Dörner, J. Stohner, J. Kiedrowski, M. Reggelin, S. Marquardt, A. Schießer, R. Berger, and M. S. Schöffler, Direct determination of absolute molecular stereochemistry in gas phase by coulomb explosion imaging, Science 341, 1096 (2013).
- A. Pier, K. Fehre, S. Grundmann, I. Vela-Perez, N. Strenger, M. Kircher, D. Tsitsonis, J. B. Williams, A. Senftleben, T. Baumert, M. S. Schöffler, P. V. Demekhin, F. Trinter, T. Jahnke, and R. Dörner, Chiral photoelectron angular distributions from ionization of achiral atomic and molecular species, Phys. Rev. Res. 2, 033209 (2020).
- G. Nalin et al., Photoelectron circular dichroism of O 1s-photoelectrons of uniaxially oriented trifluoromethyloxirane: energy dependence and sensitivity to molecular configuration, Phys. Chem. Chem. Phys. 23, 17248 (2021).
- K. Fehre et al., Fourfold differential photoelectron circular dichroism, Phys. Rev. Lett. 127, 103201 (2021).
- Y.-I. Suzuki, Wave packet simulations for molecular orientation induced by circularly polarized light: Toward chiral resolution in the gas phase, Chem. Phys. Lett. 785, 139134 (2021).
- L. D. Barron, Molecular Light Scattering and Optical Activity, 2nd ed. (Cambridge University, New York, 2009).
- M. Curie, Pierre Curie (Dover, New York, 1963).
- P. Curie, Sur la symétrie dans les phénomènes physiques, symétrie d'un champ électrique et d'un champ magnétique, J. Phys. Theor. Appl. 3, 393 (1894).
- R. E. Newnham, Properties of Materials: Anisotropy, Symmetry, Structure (Oxford University, New York, 2005).
- S. T. Lagerwall, Ferroelectric and Antiferroelectric Liquid Crystals (Wiley, New York, 1999).
- R. R. Birss, Symmetry and Magnetism, 2nd ed. (North-Holland, Amsterdam, 1966).
- A. S. Nowick, Crystal Properties via Group Theory (Cambridge University, New York, 1995).
- R. R. Lucchese, A simple model for molecular frame photoelectron angular distributions, J. Electron Spectrosc. 141, 201 (2004).
- D. Dowek, M. Lebech, J. C. Houver, and R. R. Lucchese, Circular dichroism in molecular frame photoemission, Mol. Phys. 105, 1757 (2007).
- K. Mislow, Molecular chirality, in Topics in Stereochemistry (Wiley, New York, 1999), pp. 1–82.
- D. M. Brink and G. R. Satchler, Angular Momentum, 2nd ed., Oxford Library of the Physical Sciences (Clarendon, Oxford, 1968).
- V. L. Jacobs, Theory of atomic photoionization measurements, J. Phys. B 5, 2257 (1972).
- K. Bonhoff, S. Nahrup, B. Lohmann, and K. Blum, Angular distribution of molecular Auger electrons, J. Chem. Phys. 104, 7921 (1996).
- S. Motoki, J. Adachi, K. Ito, K. Ishii, K. Soejima, A. Yagishita, S. K. Semenov, and N. A. Cherepkov, Complete photoionization experiment in the region of the shape resonance of the molecule, J. Phys. B 35, 3801 (2002).
- A. N. Grum-Grzhimailo, On the angular distributions in molecular photoionization beyond the dipole approximation, J. Phys. B 36, 2385 (2003).
- Y.-I. Suzuki and T. Suzuki, Determination of ionization dynamical parameters by time-resolved photoelectron imaging, Mol. Phys. 105, 1675 (2007).
- Similarly, it is possible to define a chiral molecule by a point group such that the pseudoscalar, the parity-odd rank zero tensor, is totally symmetric.
- This is an addition of two contragredient tensors [52] and , resulting in a contragredient tensor . Here, a contragredient tensor can be defined by a complex conjugate of a tensor , a cogredient tensor, where . They obey the transformation rules for the rotation defined by the Euler angles , and , using rotation matrices. The last equation indicates that is a cogredient tensor of rank and component , and hence is a contragredient tensor of rank 1 and component . In addition, a minus sign is added for to make positive.
- C. N. Yang, On the angular distribution in nuclear reactions and coincidence measurements, Phys. Rev. 74, 764 (1948).
- U. Fano and D. Dill, Angular momentum transfer in the theory of angular distributions, Phys. Rev. A 6, 185 (1972).
- Y.-I. Suzuki, Improved chiral photoelectron spectroscopy via selection of chirality-selective molecular axis orientations: A theoretical analysis of non-negative smooth functions, Phys. Rev. Lett. 130, 143202 (2023).
- J. Cooper and R. N. Zare, Angular distribution of photoelectrons, J. Chem. Phys. 48, 942 (1968).
- U. Fano, Spin orientation of photoelectrons ejected by circularly polarized light, Phys. Rev. 178, 131 (1969).
- J. Kessler and J. Lorenz, Experimental verification of the Fano effect, Phys. Rev. Lett. 24, 87 (1970).
- K. Soejima, A. Danjo, K. Okuno, and A. Yagishita, Linear and circular dichroism in the double photoionization of helium, Phys. Rev. Lett. 83, 1546 (1999).
- O. Geßner, Y. Hikosaka, B. Zimmermann, A. Hempelmann, R. R. Lucchese, J. H. D. Eland, P.-M. Guyon, and U. Becker, inner valence photoionization dynamics of NO derived from photoelectron-photoion angular correlations, Phys. Rev. Lett. 88, 193002 (2002).
- A. F. Ordonez and O. Smirnova, Disentangling enantiosensitivity from dichroism using bichromatic fields, Phys. Chem. Chem. Phys. 24, 7264 (2022).
- R. S. Cahn, C. Ingold, and V. Prelog, Specification of molecular chirality, Angew. Chem., Int. Ed. Engl. 5, 385 (1966).
- K. Mislow and J. Siegel, Stereoisomerism and local chirality, J. Am. Chem. Soc. 106, 3319 (1984).
- These axes are defined by and axes of inertia for methyloxirane and (a nonchiral isotopomer), respectively.
- See Supplemental Material at http://link.aps.org/supplemental/10.1103/PhysRevA.109.L060802 for details of the symmetry of , implications for photoelectron spin, additional figures for methyloxirane, which includes Refs. [77, 78, 79, 80, 81, 82, 83, 84, 85].
- L. Barron, Optical activity and time reversal, Mol. Phys. 43, 1395 (1981).
- Y.-I. Suzuki, Communication: Photoionization of degenerate orbitals for randomly oriented molecules: The effect of time-reversal symmetry on recoil-ion momentum angular distributions, J. Chem. Phys. 148, 151101 (2018).
- D. Dill and J. L. Dehmer, Electron-molecule scattering and molecular photoionization using the multiple-scattering method, J. Chem. Phys. 61, 692 (1974).
- Y.-I. Suzuki and T. Suzuki, Photoelectron angular distribution in valence shell ionization of heteroaromatic molecules studied by the continuum multiple scattering method, J. Phys. Chem. A 112, 402 (2008).
- R. N. Zare, Angular Momentum: Understanding Spatial Aspects in Chemistry and Physics (Wiley, New York, 1988).
- D. Dill, Fixed-molecule photoelectron angular distributions, J. Chem. Phys. 65, 1130 (1976).
- N. A. Cherepkov and G. Raseev, Photoionization of oriented CO molecule: Linear dichroism in the angular-distribution of photoelectrons, J. Chem. Phys. 103, 8238 (1995).
- Y. Suzuki and T. Seideman, Mapping rotational coherences onto time-resolved photoelectron imaging observables, J. Chem. Phys. 122, 234302 (2005).
- P. Hockett and V. Makhija, Topical review: Extracting molecular frame photoionization dynamics from experimental data, J. Phys. B 56, 112001 (2023).
- Y.-I. Suzuki, Circular dichroism in photoionization of degenerate orbitals: Spin-polarized photoelectrons and spontaneous separation of oriented photoions, J. Chem. Phys. 149, 204312 (2018).
- A. Gelessus, W. Thiel, and W. Weber, Multipoles and symmetry, J. Chem. Edu. 72, 505 (1995).
- Y.-I. Suzuki, Direct relation of molecular orbital symmetry with photoelectron angular distributions from aligned molecules in the gas phase, J. Phys. B 41, 215204 (2008).
- N. A. Cherepkov, Manifestations of the optical activity of molecules in the dipole photoeffect, J. Phys. B 16, 1543 (1983).