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Themed Issue in Honor of Prof. Maciej J. Nowak, for His Contributions to the Field of Photochemistry of Matrix-Isolated Species

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A special issue of Photochem (ISSN 2673-7256).

Deadline for manuscript submissions: closed (31 May 2022) | Viewed by 21226

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Prof. Dr. Rui Fausto

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Department of Chemistry, Coimbra Chemistry Center (CQC-IMS), University of Coimbra, 3004-535 Coimbra, Portugal
Interests: photochemistry; molecular cryo- and biospectroscopy; quantum chemistry; molecular structure; photophysics; chemometrics
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Prof. Dr. Robert Kołos

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Laboratory Astrochemistry Group, Institute of Physical Chemistry, Polish Academy of Sciences, Warsaw, Poland
Interests: astrochemistry; molecular spectroscopy

Special Issue Information

Dear Colleagues,

This Special Issue of Photochem is dedicated to Professor Maciej J. Nowak, for his contributions to our understanding of the photochemistry of matrix-isolated species.

Dr. Fernando Rubiera González

Professor Maciej J. Nowak was born and educated in Warsaw (Poland). He completed his MSc degree at the University of Warsaw (Department of Physics) in 1971 and started his work at the Department of Physics of the same University, in the Atomic and Molecular Optics Research Group of the Institute of Experimental Physics, where he worked on the study of molecular interactions (mainly H-bond) in solid phase and in liquids. He obtained his PhD in Physics (1979) under the supervision of Prof. Krystyna Szczepaniak at the Department of Biophysics of the same university. In his doctoral work and all along his career at the Institute of Physics of Polish Academy of Sciences (where he is still working), Prof. Nowak has revealed fundamental structural details and reactivity patterns of nucleic acid bases, initially in the gas phase, and most of the time using the matrix isolation method as the main research technique, together with infrared spectroscopy. Prof. Nowak was one of the pioneers in Europe on the use of matrix isolation spectroscopy to look at photochemistry reactions, in particular those involving nucleic acid bases and related compounds.

He has been awarded an Alexander von Humbodt fellowship that allowed him to spend two years (1981–1982) at the Department of Physical Chemistry in the research group of Prof. Werner A. P. Luck, after which he established a modern laboratory for matrix-isolation studies at the Institute of Physics PAS in Warsaw, which he has led since 1986. In his habilitation, Prof. Nowak focused on the determination of the structure of the most stable forms of the isolated nucleic acid bases: uracil, thymine, cytosine, and adenine isolated in the low-temperature matrix, publishing some of the most complete and seminal research on these chemical systems. In 2010, he obtained the title of Professor in Physics, starting to work as a full professor in the Institute of Physics PAS. In 2019, he retired but continued working part-time in the Institute.

Prof. Nowak has published 125 articles in the most prestigious scientific journals, where he has reported the results of his research. In one of his first articles (together with the group of Prof. William B. Person), he demonstrated, for the first time, the successful application of ab initio (HF) calculations to IR spectroscopy of heterocyclic molecules. Today, the calculations of vibrational spectra is a common procedure in spectroscopy research. Later on, as a result of a collaboration with Profs. Ludwik Adamowicz and Andrzej Leś, Prof. Maciej Nowak published a long series of articles where enthalpy differences between the tautomers of the nucleic acid bases and related compounds, some species being the products of photoexcitation of more stable precursors isolated in cryogenic matrices, were obtained. Additionally, in collaboration with Prof. Andrzej L. Sobolewski, a specialist of quantum chemical calculations of the excited states of the molecules, he presented new perspectives of photoreactivity in different chemical systems, including his alma mater substances, nucleic acid bases. During the last 20 years, a long-lasting and fruitful collaboration has been established between the groups of Prof. Nowak and Prof. Rui Fausto (University of Coimbra, Portugal), with the particular involvement of Drs. Leszek Lapinski (from Warsaw) and Igor Reva (from Coimbra). Particularly important results obtained from this collaboration were the identification of cytosine isomers and interconversion between cytosine isomers induced by UV or NIR irradiation, the investigation of the effects of NIR selective excitation of overtone vibrations of isolated flexible molecules leading to conformational changes, and the direct observation of different chemical processes taking place via the quantum mechanical tunneling effect. More recently, Prof. Nowak has also been interested in investigations of the influence of solid hydrogen matrix environments on the course of H-atom-transfer oxo → hydroxy and thion → thiol phototautomeric processes occurring (or not occurring) in oxo and thio compounds isolated in Ar and H2 matrices.

Although the home Institute of Prof. Maciej Nowak is not dedicated to education, he has been involved in teaching university students and has been engaged in the education of PhD students from his own laboratory, his Institute and from Warsaw PhD School. In his own words, “my passion is the experiment”, and during his whole career, he was actively engaged in constructing experimental equipment, preparing experiments, and working with experiments, usually with the support and help of Drs. Leszek Lapinski and Hanna Rostkowska, his long-standing co-workers (and good friends) at the Physics Institute PAS.

We are very pleased to give all colleagues and friends of Profesor Maciej J. Nowak the opportunity to celebrate his scientific career by contributing to this Special Issue dedicated to honoring his achievements in the field of photochemistry of matrix-isolated species.

Prof. Dr. Rui Fausto
Prof. Dr. Robert Kołos
Guest Editors

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Keywords

photochemistry
matrix-isolated species
infrared spectroscopy
quantum chemical calculations
nucleic acid bases

Published Papers (10 papers)

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Research

12 pages, 3171 KiB

Open AccessArticle

Mass-Resolved Momentum Imaging of Three Dichloroethylene Isomers by Femtosecond Laser-Induced Coulomb Explosion

by Yoriko Wada, Hiroshi Akagi, Takayuki Kumada, Ryuji Itakura and Tomonari Wakabayashi

Photochem 2022, 2(3), 798-809; https://doi.org/10.3390/photochem2030051 - 16 Sep 2022

Cited by 1 | Viewed by 2386

Abstract

Coulomb explosion experiments using linearly polarized intense 60 fs laser pulses were conducted for structural characterization of three dichloroethylene (DCE) isomers, 1,1-DCE, cis-1,2-DCE, and trans-1,2-DCE. Under relatively low laser intensity at 1.8 × 10¹⁴ W/cm², mass-resolved momentum imaging (MRMI) for selected fragment ions of ³⁵Cl⁺ and C²⁺ revealed different patterns for the three isomers. The C²⁺ ion fragmented from multiply charged trans-1,2-DCE was forced to leave perpendicularly to the direction of the laser polarization, due to recoil forces from adjacent cations. In contrast, the fast ions of C²⁺ from cis-1,2-DCE exhibited an isotropic distribution, whereas the fast ions of C²⁺ from 1,1-DCE recoiled along the laser polarization together with the slow C²⁺ ions, and thereby distinction of the three isomers was demonstrated. Coulomb explosion occurs predominantly at specific orientation, which is useful for potential applications of MRMI analysis to molecular structure assays. Full article

(This article belongs to the Special Issue Themed Issue in Honor of Prof. Maciej J. Nowak, for His Contributions to the Field of Photochemistry of Matrix-Isolated Species)

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17 pages, 1531 KiB

Open AccessArticle

Vibrational-Excitation-Induced and Spontaneous Conformational Changes in Solid Para-H₂—Diminished Matrix Effects

by Sándor Góbi, Gopi Ragupathy, Gábor Bazsó and György Tarczay

Photochem 2022, 2(3), 563-579; https://doi.org/10.3390/photochem2030039 - 26 Jul 2022

Cited by 3 | Viewed by 1514

Abstract

Both vibrational-excitation-induced (by (N)IR laser) and spontaneous (by H atom tunneling) conformational changes are often investigated by matrix-isolation spectroscopy. It is well known that rigid hosts, such as solid noble gases, N₂, or normal-H₂, can largely affect both the quantum efficiency of the (N)IR photon-induced process and the tunneling rate. In the present study, the conformational changes of formic and acetic acids, as well as glycine, were investigated in a soft quantum host, solid para-H₂. It is shown that the tunneling rates in para-H₂ are orders of magnitude larger than those in rigid hosts. Furthermore, our results also suggest that the quantum efficiencies of some (N)IR-light-induced conformational changes are larger than in rigid matrices. These results can open a door for the applications of para-H₂ host in conformational and tunneling studies and can help understand the details of these complex processes. Full article

(This article belongs to the Special Issue Themed Issue in Honor of Prof. Maciej J. Nowak, for His Contributions to the Field of Photochemistry of Matrix-Isolated Species)

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15 pages, 6645 KiB

Open AccessArticle

Phototransformations of 2,3-Diamino-2-Butenedinitrile (DAMN) Monomers Isolated in Low-Temperature Argon Matrix

by Igor Reva, Hanna Rostkowska and Leszek Lapinski

Photochem 2022, 2(2), 448-462; https://doi.org/10.3390/photochem2020031 - 16 Jun 2022

Viewed by 1531

Abstract

UV-induced transformations were studied for monomers of 2,3-diamino-2-butenedinitrile (DAMN) isolated in argon matrices. Photoinduced hydrogen-atom transfer was found to be the major process occurring upon UV (λ > 320 nm or λ > 295 nm) excitation of matrix-isolated DAMN monomers. As a result of the transfer of a hydrogen atom from an amino group to a nitrile fragment, a tautomer of DAMN involving a ketenimine group was generated. Identification of this photo-produced species was based on comparison of its experimental IR spectrum with the spectrum theoretically predicted for the ketenimine form. Another product photogenerated upon UV (λ > 320 nm, λ > 295 nm, or λ > 270 nm) irradiation of DAMN isolated in Ar matrices was identified as 4-amino-1H-imidazole-5-carbonitrile (AICN). The structure of this photoproduct was unambiguously assigned on the basis of an exact match of wavenumbers of the bands in the IR spectrum of this photogenerated species and the wavenumbers of IR bands of AICN trapped (in a separate experiment) from the gas phase into an Ar matrix. Full article

(This article belongs to the Special Issue Themed Issue in Honor of Prof. Maciej J. Nowak, for His Contributions to the Field of Photochemistry of Matrix-Isolated Species)

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13 pages, 1799 KiB

Open AccessArticle

UV-Vis Spectrophotometer as an Alternative Technique for the Determination of Hydroquinone in Vinyl Acetate Monomer

by Md Al Mamunur Rashid, Mofizur Rahman, ASM Obaidullah Mahmud, Ali Shazzad Mohammad Morshed, Md Masudul Haque and Md Mobarak Hossain

Photochem 2022, 2(2), 435-447; https://doi.org/10.3390/photochem2020030 - 15 Jun 2022

Cited by 5 | Viewed by 2986

Abstract

As an appropriate quantity of hydroquinone (HQ) is essential to safeguard inhibition characteristics by eliminating the risk of self-polymerization of vinyl acetate monomer (VAM), the determination of the HQ content in VAM is very crucial to ensure the stability of VAM during storage and transportation as well as to achieve the possibility of a proper polymerization reaction. In this study, a simple, cheap, time-saving, and easy method has been developed by which the HQ content in VAM can be measured quickly based on the measurement of UV-Vis absorbance of the HQ content at 293 nm using methanol as a blank. No color development is required for this determination process, and the HQ content in the VAM can be measured directly without any further processing. The limit of detection, limit of quantification, linearity range, accuracy, precision, robustness, and measurement uncertainty of this method have been measured and analyzed and found to be within the acceptable limit and range. The method shows linearity within 0.36–25.0 ppm HQ content in the solution range with a regression coefficient of 0.9999, a relative spike recovery of 101.35%, precision of 1.36%, relative bias of 0.55%, and robustness with a temperature variation of −5 °C. Full article

(This article belongs to the Special Issue Themed Issue in Honor of Prof. Maciej J. Nowak, for His Contributions to the Field of Photochemistry of Matrix-Isolated Species)

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14 pages, 2393 KiB

Open AccessArticle

UV-Induced Benzyloxy Rotamerization in an Ortho OH-Substituted Aryl Schiff Base

by İsa Sıdır, Yadigar Gülseven Sıdır, Sándor Góbi, Halil Berber and Rui Fausto

Photochem 2022, 2(2), 376-389; https://doi.org/10.3390/photochem2020026 - 25 May 2022

Viewed by 1687

Abstract

A new benzyloxy containing ortho hydroxyl-substituted aryl Schiff base, trans 2-((2-(benzyloxy)benzylidene) amino)phenol (abbreviated as BBAP), was synthesized and characterized by ¹H-, ¹³C-NMR and infrared spectroscopic techniques and elemental analysis. The conformational landscape of the compound, as well as its infrared spectra in argon and N₂ cryogenic matrices (10 K) were investigated, followed by the study of the effects of in situ UV irradiation of the matrix-isolated compound. The structural information was obtained through an extensive series of quantum chemical calculations performed at the DFT(B3LYP)/6-311++G(d,p) level of theory, which enabled to identify 3 low-energy OH···N intramolecularly H-bonded conformers of the molecule that were later found to be present in the as-deposited cryogenic matrices. The 3 experimentally relevant conformers of BBAP differ in the geometry of the benzyloxy substituent, and were discovered to interconvert upon in situ UV irradiation (λ = 230 nm) of the matrix-isolated compound. This is the first report on UV-induced conformational changes taking place in a benzyloxy fragment for a matrix-isolated compound. Full article

(This article belongs to the Special Issue Themed Issue in Honor of Prof. Maciej J. Nowak, for His Contributions to the Field of Photochemistry of Matrix-Isolated Species)

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9 pages, 1605 KiB

Open AccessArticle

Energy Relaxation of Porphycene in Atomic and Molecular Cryogenic Matrices

by Jacek Dobkowski, Igor V. Sazanovich, Aleksander Gorski and Jacek Waluk

Photochem 2022, 2(2), 299-307; https://doi.org/10.3390/photochem2020021 - 06 Apr 2022

Viewed by 1684

Abstract

The kinetics of relaxation of high-lying electronic states of porphycene (porphyrin isomer) embedded in different cryogenic matrices were studied using picosecond time-resolved fluorescence (TRF) and transient absorption (TA) techniques. The molecule was excited into the Soret band, i.e., with a large energy excess compared to that of the lowest (Q) excited state. The TRF and TA time profiles obtained for porphycene embedded in argon and methane matrices were remarkably different: the overall relaxation in argon occurred in 64 ps, whereas the corresponding value for methane matrix was 18 ps. Analysis of the evolution over time of different spectral ranges of TRF spectra indicates the multidimensional character of relaxation kinetics. Full article

(This article belongs to the Special Issue Themed Issue in Honor of Prof. Maciej J. Nowak, for His Contributions to the Field of Photochemistry of Matrix-Isolated Species)

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9 pages, 888 KiB

Open AccessArticle

Phosphorescence of C₅N⁻ in Rare Gas Solids

by Urszula Szczepaniak, Robert Kołos, Jean-Claude Guillemin and Claudine Crépin

Photochem 2022, 2(2), 263-271; https://doi.org/10.3390/photochem2020019 - 28 Mar 2022

Viewed by 1438

Abstract

Phosphorescence of C₅N⁻ was discovered following the ArF-laser (193 nm) photolysis of cyanodiacetylene (HC₅N) isolated in cryogenic argon, krypton, and xenon matrices. This visible emission, with an origin around 460 nm, is vibrationally resolved, permitting the measurement of frequencies for eight ground-state fundamental vibrational modes, including the three known from previous IR absorption studies. Phosphorescence lifetime amounts to tens or even hundreds of ms depending on the matrix host; it is five times longer than in the case of HC₅N. Full article

(This article belongs to the Special Issue Themed Issue in Honor of Prof. Maciej J. Nowak, for His Contributions to the Field of Photochemistry of Matrix-Isolated Species)

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26 pages, 3142 KiB

Open AccessArticle

Water Clusters in Interaction with Corannulene in a Rare Gas Matrix: Structures, Stability and IR Spectra

by Heloïse Leboucher, Joëlle Mascetti, Christian Aupetit, Jennifer A. Noble and Aude Simon

Photochem 2022, 2(2), 237-262; https://doi.org/10.3390/photochem2020018 - 25 Mar 2022

Cited by 4 | Viewed by 2374

Abstract

The interaction of polycyclic aromatic hydrocarbons (PAHs) with water is of paramount importance in atmospheric and astrophysical contexts. We report here a combined theoretical and experimental study of corannulene-water interactions in low temperature matrices and of the matrix’s influence on the photoreactivity of corannulene with water. The theoretical study was performed using a mixed density functional based tight binding/force field approach to describe the corannulene-water clusters trapped in an argon matrix, together with Born-Oppenheimer molecular dynamics to determine finite-temperature IR spectra. The results are discussed in the light of experimental matrix isolation FTIR spectroscopic data. We show that in the solid phase,

π

isomers of (C

_{20}

_{10}

)(H

_{2}

_{n}

, with n = 2 or 3, are energetically favored. These

π

complexes are characterized by small shifts in corannulene vibrational modes and large shifts in water bands. These

π

structures, particularly stable in the case of the water trimer where the water cluster is trapped “inside” the corannulene bowl, may account for the difference in photoreactivity of non-planar–compared to planar–PAHs with water. Indeed, planar PAHs such as pyrene and coronene embedded in H

_{2}

O:Ar matrices form

σ

isomers and react with water to form alcohols and quinones under low energy UV irradiation, whereas no photoreactivity was observed for corannulene under the same experimental conditions. Full article

(This article belongs to the Special Issue Themed Issue in Honor of Prof. Maciej J. Nowak, for His Contributions to the Field of Photochemistry of Matrix-Isolated Species)

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21 pages, 5839 KiB

Open AccessArticle

Phosphorescence of Hydrogen-Capped Linear Polyyne Molecules C₈H₂, C₁₀H₂ and C₁₂H₂ in Solid Hexane Matrices at 20 K

by Tomonari Wakabayashi, Urszula Szczepaniak, Kaito Tanaka, Satomi Saito, Keisuke Fukumoto, Riku Ohnishi, Kazunori Ozaki, Taro Yamamoto, Hal Suzuki, Jean-Claude Guillemin, Haruo Shiromaru, Takeshi Kodama and Miho Hatanaka

Photochem 2022, 2(1), 181-201; https://doi.org/10.3390/photochem2010014 - 28 Feb 2022

Cited by 1 | Viewed by 2460

Abstract

Laser-ablated polyyne molecules, H(C≡C)_nH, were separated by size in solutions and co-condensed with excess hexane molecules at a cryogenic temperature of 20 K in a vacuum system. The solid matrix samples containing C₈H₂, C₁₀H₂, and C₁₂H₂ molecules were irradiated with UV laser pulses and the phosphorescence 0–0 band was observed at 532, 605, and 659 nm, respectively. Vibrational progression was observed for the symmetric stretching mode of the carbon chain in the ground state with increments of ~2190 cm⁻¹ for C₈H₂, ~2120 cm⁻¹ for C₁₀H₂, and ~2090 cm⁻¹ for C₁₂H₂. Temporal decay analysis of the phosphorescence intensity revealed the lifetimes of the triplet state as ~30 ms for C₈H₂, ~8 ms for C₁₀H₂, and ~4 ms for C₁₂H₂. The phosphorescence excitation spectrum reproduces UV absorption spectra in the hexane solution and in the gas phase at ambient temperature, although the excitation energy was redshifted. The symmetry-forbidden vibronic transitions were observed for C₁₀H₂ by lower excitation energies of 25,500–31,000 cm⁻¹ (320–390 nm). Detailed phosphorescence excitation patterns are discussed along the interaction of the polyyne molecule and solvent molecules of hexane. Full article

(This article belongs to the Special Issue Themed Issue in Honor of Prof. Maciej J. Nowak, for His Contributions to the Field of Photochemistry of Matrix-Isolated Species)

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15 pages, 8187 KiB

Open AccessArticle

Observation of Light-Induced Reactions of Olefin–Ozone Complexes in Cryogenic Matrices Using Fourier-Transform Infrared Spectroscopy

by Fumiyuki Ito

Photochem 2022, 2(1), 150-164; https://doi.org/10.3390/photochem2010012 - 24 Feb 2022

Cited by 1 | Viewed by 1919

Abstract

Each olefin (ethylene, trans-1,3-butadiene, isoprene, dimethyl butadiene (DMB)) and ozone molecules were codeposited on a CsI window at cryogenic temperature, and the products of photolysis with ultraviolet–visible light were observed using Fourier-transform infrared spectroscopy. The products of the C₂H₄–O₃ system could be assigned to glyoxal (CHO–CHO), ethylene oxide (c–C₂H₄O), CO, and CO₂. The formation of CHO–CHO and c–C₂H₄ and the absence of H₂CO and HCOOH indicated that the main reaction channels did not involve C–C bond breaking. Based on this simple scheme, the photoproducts of different olefin–O₃ systems were assigned, and the vibrational features predicted by density functional theory calculations were compared with the observed spectra. Regarding butadiene, spectral matches between the observations and calculations seemed reasonable, while assignments for isoprene ambiguities of and DMB remain, mainly because of the limited availability of authentic sample spectra. Full article

(This article belongs to the Special Issue Themed Issue in Honor of Prof. Maciej J. Nowak, for His Contributions to the Field of Photochemistry of Matrix-Isolated Species)

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