Dynamic aspirin - molecular vibrations drive electrons over large distances

Aspirin is not only an important drug but also an interesting physics model system in which molecular vibrations and electrons are coupled in a particular way. For the first time, x-ray experiments in the ultrashort time domain make electron motions visible in real time. They demonstrate that very small atomic displacements shift electrons over much larger distances within the aspirin molecules.

Aspirin pills (Figure 1a) consist of many small crystallites in which molecules of acetylsalicylic acid form a regular spatial arrangement (Figure 1b). The molecules couple to each other via comparably weak interactions and generate electric fields which exert a force on the electrons of every molecule. Upon excitation of molecular vibrations, the distribution of electrons in space and, thus, the chemical properties should change. While this scenario has been a subject of theoretical work, there has been no experimental demonstration and understanding of the molecular dynamics so far.

Scientists of the Max Born Institute in Berlin, Germany, have now gained the first and direct insight in electrons motions during a coupled vibration of the aspirin molecules. In a recent issue of the journal Structural Dynamics [6,014503 (2019)], they report results of an x-ray experiment in the ultrashort time domain. An ultrashort optical pump pulse induces vibrations of the aspirin molecules with a vibrational period of approximately 1 picosecond (ps, a millionth of a millionth of a second). An ultrashort hard x-ray pulse, which is delayed relative to the pump pulse, is diffracted from the excited powder of crystallites to map the momentary spatial arrangement of electrons via an x-ray diffraction pattern.

Movie: (a) Aspirin pills. (b) Crystal structure of aspirin representing a regular, spatially periodic arrangement of molecules. (c) The animation illustrates the redistribution of electron density during the rotation of the methyl group with a period of approximately 1 ps. A single aspirin molecule is shown in a ball and stick model, the electron density as a so-called isosurface. The isosurface contains all spatial positions at which the electron density has a particular (fixed) value of 1800 elementary charges per nanometer (1800 e-/nm3). Changes of electron density result in changes of the shape of the isosurface. A shrinking around a particular atom illustrates a loss of electronic charge while an expansion reflects an increase of charge density. In the aspirin molecule, continuous periodic charge motions occur during the methyl rotation, in particular between the atoms of the carbon 6-ring (left) and the COOH carboxy unit (right).

The animation in Figure 1c shows the rotational motion of the methyl (CH3) group of an aspirin molecule which arises upon vibrational excitation. In the animation, the atomic displacements are artificially enlarged to make them visible. The methyl rotation is connected with a spatial shift of electrons over the entire aspirin molecule (yellow clouds, so-called isosurface of constant electron density). The periodic electron motions occur in time with the vibrational motions of the atoms and the distances traveled by the electrons are typically 10000 times larger than the atom displacements in the methyl rotation. This behavior demonstrates the hybrid character of the methyl rotation which is comprised of both atomic and electron motions on totally different length scales. The hybrid character originates from the electric interaction between the aspirin molecules and the dynamic minimization of electrostatic energy in the crystallite.

These new results underline the central role of hybrid modes for the stabilization of the crystal structure, in agreement with theoretical calculations. In the case of aspirin, this property favors the so-called form 1 of the crystal structure compared to other molecular arrangements. The strong modulation of the electron distribution by vibrations is relevant for numerous crystal structures in which electric interactions prevail. Vibrational excitations of ferroelectric materials should allow for an ultrafast switching of the macroscopic electric polarization and, thus, lead to new electronic devices for extremely high frequencies.

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A1-P-2025.01
Melting, bubblelike expansion, and explosion of superheated plasmonic nanoparticles

S. Dold, T. Reichenbach, A. Colombo, J. Jordan, I. Barke, P. Behrens, N. Bernhardt, J. Correa, S. Düsterer, B. Erk, T. Fennel, L. Hecht, A. Heilrath, R. Irsig, N. Iwe, P. Kolb, B. Kruse, B. Langbehn, B. Manschwetus, P. Marienhagen, F. Martinez, K.-H. Meiwes-Broer, K. Oldenburg, C. Passow, C. Peltz, M. Sauppe, F. Seel, R. M. P. Tanyag, R. Treusch, A. Ulmer, S. Walz, M. Moseler, T. Möller, D. Rupp, B. v. Issendorff

Physical review letters 134 (2025) 136101/1-7

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A3-P-2025.01
Second-harmonic generation in OP-GaAs0.75P0.25 heteroepitaxially grown from the vapor phase

L. Wang, S. R. Vangala, S. Popien, M. Beutler, J. M. Mann, V. L. Tassev, E. Büttner, V. Petrov

CrystEngComm 27 (2025) 1373-1376

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A3-P-2025.02
Diode-pumped Kerr-lens mode-locked Yb:MgWO4 laser

H.-Y. Nie, Z.-L. Lin, P. Loiko, H.-J. Zeng, L. Zhang, Z. Lin, G. Z. Elabedine, X. Mateos, V. Petrov, G. Zhang, W. Chen

Optics Letters 50 (2025) 1049-1052

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A3-P-2025.03
Growth, anisotropy, and spectroscopy of Tm3+ and Yb3+ doped MgWO4 crystals

G. Z. Elabedine, R. M. Solé, S. Slimi, M. Aguiló, F. Díaz, W. Chen, V. Petrov, X. Mateos

CrystEngComm 27 (2025) 1619-1631

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A3-P-2025.04
Growth, structure, spectroscopic, and laser properties of Ho-doped yttrium gallium garnet crystal

S. Slimi, H. Yu, H. Zhang, C. Kränkel, P. Loiko, R. M. Solé, M. Aguiló, F. Díaz, W. Chen, U. Griebner, V. Petrov, X. Mateos

Optics Express 33 (2025) 2529-2541

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A3-P-2025.05
Growth, spectroscopy and laser operation of disordered Tm,Ho:NaGd (MoO4)2 crystal

G. Z. Elabedine, Z. Pan, P. Loiko, H. Chu, D. Li, K. Eremeev, K. Subbotin, S. Pavlov, P. Camy, A. Braud, S. Slimi, R. M. Solé, M. Aguiló, F. Díaz, W. Chen, U. Griebner, V. Petrov, X. Mateos

Journal of Alloys and Compounds 1020 (2025) 179211/1-12

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A3-P-2025.06
Kerr-lens mode-locked, diode-pumped Yb,Gd:YAP laser generating 23 fs pulses

H.-Y. Nie, P. Zhang, P. Loiko, Z.-L. Lin, H.-J. Zeng, G. Zhang, Z. Li, X. Mateos, H.-C. Liang, V. Petrov, Z. Chen, W. Chen

Optics Express 33 (2025) 11793-11799

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A3-P-2025.07
Nanoindentation and laser-induced optical damage tests of CdSe nonlinear crystals

G. Exner, A. Carpenter, K. Cissner, A. Hildenbrand-Dhollande, S. Schmitt, A. Grigorov, M. Piotrowski, S. Guha, V. Petrov

Journal of the Optical Society of America B 42 (2025) A10-A14

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A3-P-2025.08
Phase-matching properties of AgGa(Se1-xTex)2 for SHG of a CO2 laser

K. Kato, V. Petrov, K. Miyata

Proceedings of SPIE 13347 (2025) 133470S/1-4

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A3-P-2025.09
Phase-matching properties of ZnSiAs2 in the mid-IR

T. Okamoto, N. Umemura, K. Kato, V. Petrov

Proceedings of SPIE 13347 (2025) 133470C/1-5

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A3-P-2025.10
Direct generation of 3.5 optical-cycle pulses from a rare-earth laser

N. Zhang, Y. Wang, H. Ding, F. Liang, Y. Zhao, J. Xu, H. Yu, H. Zhang, V. Petrov

Optics Letters 50 (2025) 3150-3153

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A3-P-2025.11
Power scaling of a non-resonant optical parametric oscillator based on periodically poled LiNbO3 with spectral narrowing

S. Das, T. Temel, G. Spindler, A. Schirrmacher, I. B. Divliansky, R. T. Murray, M. Piotrowski, L. Wang, W. Chen, O. Mhibik, V. Petrov

Optics Express 33 (2025) 5662-5669

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A3-P-2025.12
Sub-40-fs diode-pumped ytterbium-doped mixed rare-earth calcium oxoborate laser

H.-J. Zeng, Z.-L. Lin, H. Lin, P. Loiko, L. Zhang, Z. Lin, H.-C. Liang, X. Mateos, V. Petrov, G. Zhang, W. Chen

Optics Express 33 (2025) 17965-17975

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A3-P-2025.13
Spectroscopy and SESAM mode-locking of a disordered Yb:Gd2SrAl2O7 crystal

H.-J. Zeng, Z.-L. Lin, P. Loiko, F. Yuan, G. Zhang, Z. Lin, X. Mateos, V. Petrov, W. Chen

Optics Express 33 (2025) 15057-15066

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A3-P-2025.14
Watt-level, 1.6 ps χ(2)-lens mode-locking of an in-band pumped Nd:LuVO4 laser

H. Iliev, V. Aleksandrov, V. Petrov, L. S. Petrov, H. Zhang, H. Yu, I. Buchvarov

Optics Express 33 (2025) 17773-17781

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A3-P-2025.15
Refined phase-matching predictions for AgGa1-xInxS2 mixed chalcopyrite crystals

K. Kato, K. Miyata, V. Petrov

Journal of the Optical Society of America B 42 (2025) A6-A9

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A3-P-2025.16
35-fs diode-pumped mode-locked ytterbium-doped multi-component alkaline-earth fluoride laser

Z. Zhang, Z.-Q. Li, P. Loiko, H.-J. Zeng, G. Zhang, Z.-L. Lin, S. Normani, A. Braud, F. Ma, X. Mateos, H.-C. Liang, V. Petrov, D. Jiang, L. Su, W. Chen

Optics Letters 50 (2025) 1835-1838

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A3-P-2025.17
Diode-pumped few-optical-cycle laser based on an ytterbium-doped disordered strontium yttrium borate crystal

H. Zeng, Z. Lin, S. Sun, P. Loiko, H. Lin, G. Zhang, Z. Lin, C. Mou, X. Mateos, V. Petrov, W. Chen

Optics Letters 50 (2025) 2203-2206

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A3-P-2025.18
Refined Sellmeier and thermo-optic dispersion formulas for CdGeAs2

K. Kato, K. Miyata, V. Petrov

Journal of the Optical Society of America B 42 (2025) A24-A28

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A3-P-2025.19
Diode-pumped mode-locked Yb:Ca3La2(BO3)4 laser generating 35 fs pulses

H.-J. Zeng, Z.-L. Lin, G. Zhang, Z. Pan, P. Loiko, X. Mateos, V. Petrov, H. Lin, W. Chen

Optics Express 33 (2025) 22988-22996

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