Linear Dichroism and Birefringence in Polarization-Modulation Pump-Probe Spectroscopy

Denis A. Volkov orcid (Login required)
Ioffe Institute, Russian Academy of Sciences, St. Petersburg, Russian Federation

Maxim V. Belashov
Ioffe Institute, Russian Academy of Sciences, St. Petersburg, Russian Federation
ITMO University, St. Petersburg, Russian Federation

Maxim E. Sasin orcid
Ioffe Institute, Russian Academy of Sciences, St. Petersburg, Russian Federation

Oleg S. Vasyutinskii orcid
Ioffe Institute, Russian Academy of Sciences, St. Petersburg, Russian Federation


Paper #9496 received 26 Jan 2026; accepted for publication 28 Apr 2026; published online 28 May 2026

DOI: 10.18287/JBPE26.12.020306

Abstract

We present the refinement of the Polarization-Modulation Pump-Probe method developed recently in our group (PCCP V. 22, 18155 (2020)) for separation and quantitative determination of linear dichroism and birefringence of the probe laser beam in biologically relevant molecules. The method was used in the study of ultrafast relaxation dynamics in the excited states of NADH in aqueous solution. The probe beam birefringence contained contributions both from resonance pump beam absorption in NADH and from nonlinear coherent effect that was attributed to the stimulated Raman scattering in water, the latter manifested as a very intense and narrow peak at sub-picosecond delay times between pump and probe pulses. The probe beam dichroism contained the contribution from the resonance pump beam absorption in NADH and practically no contribution from nonlinear coherent effects. In this case the experimental signal was approximately twice smaller than that of the birefringence case. Therefore, it was suggested that the birefringence detection allows to achieve higher sensitivity for determination of the relatively long relaxation times than the linear dichroism detection

Keywords

polarization-modulation pump-probe; linear dichroism; birefringence; NADH; Stimulated Raman Scattering

Full Text:

PDF

References


1. D. Waldeck, A. J. Cross, D. B. McDonald, and G. R. Fleming, “Picosecond pulse induced transient molecular birefringence and dichroism,” The Journal of Chemical Physics 74(6), 3381–3387 (1981).

2. D. Mcmorrow, W. Lotshaw, and G. Kenney-Wallace, “Femtosecond Optical Kerr Studies on the Origin of the Nonlinear Responses in Simple Liquids,” IEEE Journal of Quantum Electronics 24(2), 443–454 (1988).

3. J. Chesnoy, A. Mokhtari, “Resonant impulsive-stimulated Raman scattering on malachite green,” Physical Review A 38, 3566 (1988).

4. D. M. Jonas, M. J. Lang, Y. Nagasawa, T. Joo, and G. R. Fleming, “Pump-Probe Polarization Anisotropy Study of Femtosecond Energy Transfer within the Photosynthetic Reaction Center of Rhodobacter sphaeroides R26,” The Journal of Physical Chemistry 100(30), 12660–12673 (1996).

5. Q. Zhong, J. T. Fourkas, “Optical Kerr Effect Spectroscopy of Simple Liquids,” The Journal of Physical Chemistry B 112(49), 15529–15539 (2008).

6. C. W. Freudiger, M. B. J. Roeffaers, X. Zhang, B. G. Saar, W. Min, and X. S. Xie, “Optical Heterodyne-Detected Raman-Induced Kerr Effect (OHD-RIKE) Microscopy,” The Journal of Physical Chemistry B 115(18), 5574–5581 (2011).

7. E. Molotokaite, V. Kumar, C. Manzoni, D. Polli, G. Cerullo, and M. Marangoni, “Raman‐induced Kerr effect microscopy with balanced detection,” Journal of Raman Spectroscopy 44(10), 1385–1392 (2013).

8. A. Taschin, P. Bartolini, R. Eramo, R. Righini, and R. Torre, “Optical Kerr effect of liquid and supercooled water: The experimental and data analysis perspective,” The Journal of Chemical Physics 141(8), 084507 (2014).

9. M. Tros, S. Woutersen, “Polarization-modulation setup for ultrafast infrared anisotropy experiments to study liquid dynamics,” Optics Letters 40(11), 2607 (2015).

10. I. A. Gorbunova, M. E. Sasin, and O. S. Vasyutinskii, “Observation of Anisotropic Relaxation in Biological Molecules with Subpicosecond Temporal Resolution,” Technical Physics Letters 46(2), 158–160 (2020).

11. I. A. Gorbunova, M. E. Sasin, Y. M. Beltukov, A. A. Semenov, and O. S. Vasyutinskii, “Anisotropic relaxation in NADH excited states studied by polarization-modulation pump–probe transient spectroscopy,” Physical Chemistry Chemical Physics 22(32), 18155–18168 (2020).

12. A. Taschin, P. Bartolini, S. Fanetti, A. Lapini, M. Citroni, R. Righini, R. Bini, and R. Torre, “Pressure Effects on Water Dynamics by Time-Resolved Optical Kerr Effect,” The Journal of Physical Chemistry Letters 11(8), 3063–3068 (2020).

13. J. Jiang, D. Grass, Y. Zhou, W. S. Warren, and M. C. Fischer, “Beyond intensity modulation: new approaches to pump-probe microscopy,” Optics Letters 46(6), 1474 (2021).

14. M. D. Levenvon, S. S. Kano, Introduction to Nonlinear Laser Spectroscopy, Academic Press, San Diego, CA (1988). ISBN O-12-444722-8.

15. B. V. Semak, O. S. Vasyutinskii, “Linear Dichroism and Birefringence of Probe Radiation in Pump-Probe Spectroscopy of Polyatomic Molecules,” Optics and Spectroscopy 129(9), 1007–1017 (2021).

16. B. V. Semak, Y. M. Beltukov, and O. S. Vasyutinskii, “Probe Beam Dichroism and Birefringence in Stimulated Raman Scattering in Polyatomic Molecules,” ChemPhysChem 24(22), e202300405 (2023).

17. P. S. Theocaris, E. E. Gdoutos, Matrix theory of photoelasticity, Springer Series in Optical Sciences, Springer (2013). ISBN: 978-3-540-35789-6 (eBook).

18. A. Marcano, C. Loper, and N. Melikechi, “Pump–probe mode-mismatched thermal-lens Z scan,” Journal of the Optical Society of America B19(1), 119 (2002).

19. A. L. Glazov, A. D. Il’ina, A. A. Sukharev, and O. S. Vasyutinskii, “Study of the relaxation rate of photoexcited indole molecules by the interferometric pump-and-probe method at picosecond resolution,” Technical Physics Letters 43(9), 846–848 (2017).

20. R. M. A. Azzam, “Stokes-vector and Mueller-matrix polarimetry [Invited],” Journal of the Optical Society of America A 33(7), 1396–1408 (2016).




Bookmark and Share


Сontact

34 Moskovskoe shosse, Samara, 443086, Russian Federation
Email: j-bpe@ssau.ru
Phone: +7-846-267-4550
© 2014-2025 J-BPE