Kyushu University Academic Staff Educational and Research Activities Database
List of Papers
Masashi Arakawa Last modified date:2023.12.15

Assistant Professor / Physical Chemistry / Department of Chemistry / Faculty of Sciences


Papers
1. S. Kawamura, M. Yamaguchi, S. Kono, M. Arakawa, T. Yasuike, T. Horio, and A. Terasaki, Photodestruction Action Spectroscopy of Silver Cluster Anions, AgN− (N = 3–19), with a Linear Ion Trap: Observation of Bound Excited States above the Photodetachment Threshold, J. Phys. Chem. A , 10.1021/acs.jpca.3c02900, 2023.04.
2. K. Minamikawa, T. Nishizato, H. Hashimoto, K. Matsumoto, M. Arakawa, T. Horio, and A. Terasaki, Probing Superatomic Orbitals of Sc-Doped and Undoped Silver Cluster Anions via Photoelectron Angular Anisotropy, J. Phys. Chem. Lett., 10.1021/acs.jpclett.3c00538, 14, 4011-4018, 2023.04.
3. Masashi Arakawa, Naho Hayashi, Kento Minamikawa, Tasuku Nishizato, and Akira Terasaki, Exploring s–d, s–f, and d–f Electron Interactions in AgnCe+ and AgnSm+ by Chemical Reaction toward O2, Journal of Physical Chemistry A, 10.1021/acs.jpca.2c04941, 126, 6920-6926, 2022.10, We investigate gas-phase reactions of free AgnCe+ and AgnSm+ clusters with oxygen molecules to explore s–d, s–f, and d–f electron interactions in the finite size regime; a Ce atom has a 5d electron as well as a 4f electron, whereas a Sm atom has six 4f electrons without 5d electrons. In the reaction of AgnCe+ (n = 3–20), the Ce atom located on the cluster surface provides an active site except for n = 15 and 16, as inferred from the composition of the reaction products with oxygen bound to the Ce atom as well as from their relatively high reactivity. The extremely low reactivity for n = 15 and 16 is due to encapsulation of the Ce atom by Ag atoms. The minimum reactivity observed at n = 16 suggests that a closed electronic shell with 18 valence electrons is formed with a delocalized Ce 5d electron, while the localized Ce 4f electron does not contribute to the shell closure. As for AgnSm+ (n = 1–18), encapsulation of the Sm atom was observed for n ≥ 15. The lower reactivity at n = 17 than at n = 16 and 18 implies that an 18-valence-electron shell closure is formed with s electrons from Ag and Sm atoms; Sm 4f electrons are not involved in the shell closure as in the case of AgnCe+. The present results suggest that the 4f electrons tend to localize on the lanthanoid atom, whereas the 5d electron delocalizes to contribute to the electron shell closure..
4. Tetsuichiro Hayakawa; Masashi Arakawa; Kento Minamikawa; Shuhei Fujimoto; Tomoki Kawano; Akira Terasaki, Oxidation-state analysis of manganese-oxide clusters, MnxOy+ (x = 4, y = 4–7), by X-ray absorption spectroscopy, Chemical Physics Letters, in press, 2021.10.
5. T. Horio, K. Minamikawa, T. Nishizato, H. Hashimoto, K. Matsumoto, M. Arakawa, and A. Terasaki, Photoelectron imaging of size-selected metal cluster anions in a quasi-continuous mode, Review of Scientific Instruments, 2022.08, Electron counting is a concept that often governs properties of molecules, clusters, and complexes. Here we explore silver clusters doped with a transition-metal atom, where it has been an issue whether or not 3d electrons delocalize to participate in electron counting. The experiment is performed on AgNM+/􏰀 (M = Sc–Ni) clusters to examine their stability through chemical reactivity, enabling systematic control of the number of valence electrons by the cluster size, the charge state, and the transition-metal element across the periodic table. It is revealed for 18-valence-electron clusters that 3d electrons participate in electron counting to show exceptional stability only when the transition-metal atom is endohedrally doped, except for Cr and Mn doping that forces 3d electrons to localize. We thus present new entries for superatomic metal clusters as well as a geometric factor that regulates the behavior of 3d electrons in the nanoscale regime..
6. K. Minamikawa, S. Sarugaku, M. Arakawa, and A. Terasaki, Electron counting in cationic and anionic silver clusters doped with a 3d transition-metal atom: endo- vs. exohedral geometry, Physical Chemistry Chemical Physics, DOI: 10.1039/D1CP04197E, 24, 1447-1455, 2022.01, Electron counting is a concept that often governs properties of molecules, clusters, and complexes. Here we explore silver clusters doped with a transition-metal atom, where it has been an issue whether or not 3d electrons delocalize to participate in electron counting. The experiment is performed on AgNM+/􏰀 (M = Sc–Ni) clusters to examine their stability through chemical reactivity, enabling systematic control of the number of valence electrons by the cluster size, the charge state, and the transition-metal element across the periodic table. It is revealed for 18-valence-electron clusters that 3d electrons participate in electron counting to show exceptional stability only when the transition-metal atom is endohedrally doped, except for Cr and Mn doping that forces 3d electrons to localize. We thus present new entries for superatomic metal clusters as well as a geometric factor that regulates the behavior of 3d electrons in the nanoscale regime..
7. M. Arakawa, M. Horioka, K. Minamikawa, T. Kawano, and A. Terasaki, Reaction of nitric oxide molecules on transition-metal-doped silver cluster cations: Size- and dopant-dependent reaction pathways, Physical Chemistry Chemical Physics, 10.1039/D1CP02882K, 23, 22947-22956, 2021.09, We report size- and dopant-dependent reaction pathways as well as reactivity of gas-phase free AgnM+ (M = Sc–Ni) clusters interacting with NO. The reactivity of AgnM+, except for M = Cr and Mn, exhibits a minimum at a specific size, where the cluster cation possesses 18 or 20 valence electrons consisting of Ag 5s and dopant’s 3d and 4s. The product ions range from NO adducts, AgnM(NO)m+, and oxygen adducts, AgnMOm+, to NO2 adducts, AgnM(NO2)m+. At small sizes, AgnMOm+ are the major products for M = Sc–V, whereas AgnM(NO)m+ dominate the products for M = Cr–Ni in striking contrast. In both cases, these reaction products are reminiscent of those from an atomic transition metal. However, the reaction pathways are different at least for M = Sc and Ti; kinetics measurements reveal that the present oxygen adducts are formed via NO adducts, while, for example, Ti+ is known to produce TiO+ directly by reaction with a single NO molecule. At larger sizes, on the other hand, AgnM(NO2)m+ are dominantly produced regardless of the dopant element because the dopant atom is encapsulated by the Ag host; the NO2 formation on the cluster is similar to that reported for undoped Agn+..
8. T. Hayakawa, M. Arakawa, S. Kono, T. Handa, N. Hayashi, K. Minamikawa, T. Horio, and Akira Terasaki, X-ray absorption spectroscopy of small copper-oxide cluster ions for analyses of Cu oxidation state and Ar complexation: CuOAr+ and Cu2O2+, Z. Phys. Chem., 10.1515/zpch-2020-1668, 235, 213-224, 2021.02.
9. Masashi Arakawa, Masataka Horioka, Kento Minamikawa, Tomoki Kawano, and Akira Terasaki, Reaction kinetics of nitric oxide on size-selected silver cluster cations, Journal of Physical Chemistry C, 10.1021/acs.jpcc.0c08890, 124, 26881-26888, 2020.11, We report reactions of gas-phase free silver cluster cations, Agn+ (n
= 3−18), with nitric oxide molecules, which was studied by kinetics
measurements using an ion trap. AgnO(NO2)m−1+ and Agn(NO2)m+ were
observed as major products after multiple reactions. The reaction pathway to
form these product ions was identified by fitting the data to rate equations for n ≤
15, except for inert n = 3 and 5. Two different reaction mechanisms were found
for the formation of these products depending on cluster size; pseudo-first-order
rate constants of each step of elementary reactions were obtained. First, as found
for n = 4, 6, and 9, AgnO+ is formed by a reaction with two NO molecules, which
is followed by a release of neutral N2O. A further reaction of AgnO+ with another
NO molecule produces AgnNO2+. Agn(NO2)m+ (m ≥ 1) is thus successively
formed via an intermediate, AgnO(NO2)m−1+. This is analogous to the reaction of
NO on silver surfaces to produce NO2. Second, both AgnNO2+ and AgnO+ are formed concurrently, as found for n = 7, 8, 10, 11, 12, and 15; AgnO+ does not act as an intermediate for AgnNO2+. AgnO(NO2)m−1+ and Agn(NO2)m+ (m ≥ 2) are formed by successive addition of NO2 to AgnO+ and AgnNO2+, respectively. It is speculated that the successive addition of NO2 proceeds via disproportionation, i.e., three NO molecules are converted to NO2 and N2O. The reaction pathways of n = 13 and 14 are explained equally well by the two mechanisms. The overall reaction rate coefficients exhibit an odd−even alternation; the higher reactivity for even values of n is due to an odd number of valence electrons..
10. Masashi Arakawa, Daichi Okada, Satoshi Kono, and Akira Terasaki, Preadsorption effect of carbon monoxide on reactivity of cobalt cluster cations toward hydrogen, Journal of Physical Chemistry A, 10.1021/acs.jpca.0c05819, 124, 9751-9756, 2020.10, We report gas-phase reactions of free Con(CO)+m (n = 3−11, m = 0−2) with H2, expecting a catalytic reaction of coadsorbed CO and H2 on Co+n. Preadsorption of CO molecules is found to promote H2 adsorption, in particular, on Con(CO)+ (n = 5, 8−10). Density functional theory (DFT) calculations reveal that the reactivity is governed by the molecular-orbital energy of Co+n, which is tuned by preadsorbed CO molecules. Collision-induced-dissociation experiments performed on ConCOH+2 (n = 8−10) imply that at least some of the CO and H2 molecules are bound together on Co+n..
11. K. Minamikawa, M. Arakawa, K. Tono, and A. Terasaki, A revisit to electronic structures of cobalt-doped silver cluster anions by size-dependent reactivity measurement, Chemical Physics Letters, 10.1016/j.cplett.2020.137613, 753, 137613, 2020.05.
12. T. Handa, T. Horio, M. Arakawa, and A. Terasaki, Improvement of reflectron time-of-flight mass spectrometer for better convergence of ion beam, International Journal of Mass Spectrometry, 2020.03.
13. Satoshi Kono, Masashi Arakawa, Akira Terasaki, Analysis of cluster growth in magnetron-sputtering metal-cluster source by optical emission spectroscopy, Chemistry Letters, 10.1246/cl.190727, 48, 1537-1540, 2019.10.
14. Shun Sarugaku, Masashi Arakawa, Tomoki Kawano, Akira Terasaki, Electronic and geometric effects on chemical reactivity of 3d-transition-metal-doped silver cluster cations toward oxygen molecules, Journal of Physical Chemistry C, 10.1021/acs.jpcc.9b05117, 123, 25890-25897, 2019.10, We report electronic and geometric structures of 3d-transition-metal-doped silver cluster cations, AgN−1M+ (M = Sc−Ni), studied by chemical reaction with oxygen molecules. The evaluated reaction rate coefficients for small sizes, N, are 2− 6 orders of magnitude higher than those of undoped AgN+, whereas those for large N are comparable with those of AgN+. The low reactivity at large sizes is attributed to a geometric effect, that is, encapsulation of the dopant atom, which provides an active site located on the surface of the cluster in small sizes. In addition, a reactivity minimum is observed for AgN−1M+ with M = Sc, Ti, V, Fe, Co, and Ni at a specific size, where the cluster possesses 18 valence electrons including 3d electrons. With the aid of density functional theory calculations, the reactivity minimum is suggested to be due to an electronic effect, that is, formation of a closed electronic shell by the 18 valence electrons, implying delocalized 3d electrons. Ag13Cr+ and Ag12Mn+, possessing 18 valence electrons as well, are noted to be exceptions, where d electrons are supposed to be localized on the dopant atom because of the half-filled nature of Cr and Mn 3d orbital..
15. T. Ito, M. Arakawa, Y. Taniguchi, and A. Terasaki, Adsorption kinetics of nitrogen molecules on size-selected silver cluster cations, Zeitschrift für Physikalische Chemie, 10.1515/zpch-2019-1373, 233, 759-770, 2019.04.
16. Hayakawa, M. Arakawa, K. Ando, Y. Kiyomura, T. Kawano, and A. Terasaki, Charge-state analysis of small barium-oxide clusters by X-ray absorption spectroscopy, J. Phys.: Condens. Matter, 10.1088/1361-648X/aafe18, 31, 134003, 2019.03.
17. K. Ando, M. Arakawa, and A. Terasaki, Freezing of micrometer-sized liquid droplets of pure water evaporatively cooled in a vacuum, Physical Chemistry Chemical Physics, 10.1039/C8CP05955A, 20, 28435-28444, 2018.10, Freezing processes are reported for pure-water droplets generated in a vacuum in the size range of 49–71 mm in diameter. The process is characterized for each size by measurement of a freezing curve, where the fraction of frozen droplets is evaluated as a function of time. The 49 mm droplet was found to freeze at a time between 7.0 and 7.9 ms after being generated at room temperature, where the fraction of frozen droplets increased from 5% to 95%; the freezing time was thus distributed statistically within 1 ms. The freezing time was retarded by about 3 ms as the size increases from 49 to 71 mm, while the rise time of the freezing curve was almost unchanged. Numerical simulation of a cooling curve, i.e., the temperature of a droplet as a function of time, revealed that the droplets in the present size range are frozen at almost the same temperature between 233 and 236 K. The freezing curves measured in the experiment were well reproduced by numerical simulation based on the simulated cooling curves combined with the temperature dependence of the volume-based homogeneous ice nucleation rates of pure water reported previously. It was also found that a droplet is disintegrated into a few fragments upon freezing, which suggests formation of a frozen shell in the outer region of a droplet..
18. M. Arakawa, K. Ando, S. Fujimoto, S. Mishra, G. Naresh Patwari, and A. Terasaki, The role of electronegativity on the extent of nitridation of group 5 metals as revealed by reactions of tantalum cluster cations with ammonia molecules, Physical Chemistry Chemical Physics, 10.1039/c8cp00424b, 20, 13794-13982, 2018.04, Reactions of the free tantalum cation, Ta+, and tantalum cluster cations, Tan+ (n = 2–10), with ammonia are presented. The reaction of the monomer cation, Ta+, with two molecules of NH3 leads to the formation of TaN2H2+ along with release of two H2 molecules. The dehydrogenation occurs until the formal oxidation number of the tantalum atom reaches +5. On the other hand, all the tantalum cluster cations, Tan+, react with two molecules of NH3 and form TanN2+ with the release of three H2 molecules. Further exposure to ammonia showed that TanNmH+ and TanNm+ are produced through successive reactions; a pure nitride and three H2 molecules are formed for every other NH3 molecule. The nitridation occurred until the formal oxidation number of the tantalum atoms reaches +5 as in the case of TaN2H2+ in contrast to other group 5 elements, i.e., vanadium and niobium, which have been reported to produce nitrides with lower oxidation states. The present results on small gas-phase metal- nitride clusters show correlation with their bulk properties: tantalum is known to form bulk nitrides in the oxidation states of either +5 (Ta3N5) or +3 (TaN), whereas vanadium and niobium form nitrides in the oxidation state of +3 (VN and NbN). Along with DFT calculations, these findings reveal that nitridation is driven by the electron-donating ability of group 5 elements, i.e., electronegativity of the metal plays a key role in determining the composition of the metal nitrides..
19. T. Hayakawa, M. Arakawa, S. Sarugaku, K. Ando, K. Tobita, Y. Kiyomura, T. Kawano, A. Terasaki, Characterization of Cerium and Oxygen Atoms in Free Clusters of Cerium Oxide by X-ray Absorption Spectroscopy, Topics in Catalysis, 10.1007/s11244-017-0869-y, 61, 119-125, 2017.12.
20. Masashi Arakawa, Tsubasa Omoda, Akira Terasaki, Adsorption and Subsequent Reaction of a Water Molecule on Silicate and Silica Cluster Anions, Journal of Physical Chemistry C, 10.1021/acs.jpcc.6b11689, 2017.01, We present reactions of size-selected free silicate, MglSiOm−, and silica, SinOm−, cluster anions with a H2O molecule focusing on H2O adsorption. It was found that H2O adsorption to MglSiOm− with l = 2 and 3 (m = 4−6) is always followed by molecular oxygen release, whereas reactivity of the clusters with l = 1 (m = 3−5) was found to be much lower. On the contrary, in the reaction of SinOm− (n = 3−8, 2n − 1 ≤ m ≤ 2n + 2), a H2O adduct is observed as a major reaction product. Larger and oxygen- rich clusters tend to exhibit higher reactivity; the rate constants of the adsorption reaction are 2 orders of magnitude larger than those of CO adsorption previously reported. DFT calculations revealed that H2O is dissociatively adsorbed on SinOm− to form two SiO3(OH) tetrahedra. The site selectivity of H2O adsorption is governed by the location of the singly occupied molecular orbital (SOMO) on SinOm−. The present findings give molecular-level insights into H2O adsorption on silica and silicate species in the interstellar environment..
21. Shun Sarugaku, Masashi Arakawa, Akira Terasaki, Space focusing extensively spread ions in time-of-flight mass spectrometry by nonlinear ion acceleration, International Journal of Mass Spectrometry, 10.1016/j.ijms.2017.01.003, 414, 65-69, 2017.01.
22. Shun Sarugaku, R. Murakami, J. Matsumoto, T. Kawano, Masashi Arakawa, Akira Terasaki, Size-Dependent Reactivity of Nickel-Doped Silver Cluster Cations toward Oxygen: Electronic and Geometric Effects, Chemistry Letters, 10.1246/cl.161094, 46, 385-388, 2017.01.
23. Kota Ando, Masashi Arakawa, Akira TERASAKI, Evaporation processes of a liquid droplet of ethylene glycol in a vacuum, Chemistry Letters, 10.1246/cl.160381, 45, 961-963, 2016.05.
24. T. Hayakawa, K. Egashira, M. Arakawa, T. Ito, S. Sarugaku, K. Ando, A. Terasaki, X-ray absorption spectroscopy of Ce2O3+ and Ce2O5+ near Ce M-edge, Journal of Physics B, 2016.02.
25. Masashi Arakawa, Ryo Yamane, Akira Terasaki, Reaction sites of CO on size-selected silicon-oxide cluster anions: a model study of chemistry in the interstellar environment, Journal of Physical Chemistry A, 10.1021/acs.jpca.5b08900, 120, 139-144, 2016.01.
26. Hiroshi Fukazawa, Masashi Arakawa, Hiroki Yamauchi, Yurina Sekine, Riki Kobayashi, Yoshiya Uwatoko, Songxue Chi, Jaime A. Fernandez-Baca, Properties of ferroelectric ice, JPS Conference Proceeding, 8, 033010-1-033010-6, 2015.11.
27. Masashi Arakawa, Kei Kohara, Akira Terasaki, Reaction of aluminum cluster cations with a mixture of O2 and H2O gases: Formation of hydrated-alumina clusters, Journal of Physical Chemistry C, 10.1021/jp511293g, 119, 10981-10986, 2015.04, We present reactions of size-selected free aluminum cluster
cations, AlN+ (N = 1−14), exposed to a mixture of water and oxygen gases.
It is featured that chemical species assignable to Al2O6H7+ and Al2O7H9+
were commonly produced as prominent reaction products from all of the
sizes, except N = 1. These product ions were found to be produced via the
formation of Al2O3+ in the initial stage of reactions with O2 and H2O,
which was followed by successive hydrogenation and hydration. This
reaction pathway was identified by examining reactivity of each
intermediate product step by step. Structures of the product ions were
analyzed by collision-induced dissociation experiments and DFT calculations; for+ example, coexistence of isomers, Al2O5H5(H2O)+ and
Al2O4H3(H2O)2 , with one and two intact H2O molecules, respectively, was suggested for Al2O6H7+. The chemical compositions of the ions +
produced in the present reactions are expressed nominally as Al2O3(H2O)nH , which is similar, except for the proton, to that of hydrated alumina, that is, forms of bulk aluminum abundant naturally. The present finding gives molecular-level insights into formation processes of aluminum minerals in a natural environment..
28. Tomonori Ito, G. Naresh Patwari, Masashi Arakawa, Akira Terasaki, Water-induced adsorption of carbon monoxide and oxygen on the gold dimer cation, Journal of Physical Chemistry A, 10.1021/jp501111f, 2014.03.
29. Masashi Arakawa, Kei Kohara, Tomonori Ito, Akira Terasaki, Size-dependent reactivity of aluminum cluster cations toward water molecules, European Physical Journal D, 2013.04.
30. Arakawa M., Kagi H., Fernandez-Baca J. A., Chakoumakos B. C. and Fukazawa H., The existence of memory effect on hydrogen ordering in ice: The effect makes ice attractive, Geophysical Research Letters, in press, 2011.08.
31. Ishibashi H., Arakawa M., Yamamoto J. and Kagi H., Precise determination of Mg/Fe ratio applicable to terrestrial olivine using Raman spectroscopy, Journal of Raman Spectroscopy, 43, 331-337, 2012.02.
32. Fukazawa H., Arakawa M., Kagi H., Yamauchi H., Fernandez-Baca J. A., Chakoumaks B. C., Structure and Properties of Ferroelectric Water Ice, Physics and Chemistry of ice 2010 (Hokkaido University Press), 421-428, 2011.05.
33. Arakawa M., Kagi H. and Fukazawa H., Annealing effects on hydrogen ordering in KOD-doped ice observed using neutron diffraction, Journal of Molecular Structure, doi:10.1016/j.molstruc.2010.02.016, 982, 111, 2010.03.
34. Abe J., Hattori T., Komatsu K., Arima H., Arakawa M., Sano A., Kagi H., Harjo S., Ito T., Moriai A., Aizawa K., Arai M. and Utsumi W., High-pressure experiments with the engineering material diffractometer (BL-19) at J-PARC, Journal of Physics: Conference Series, 215, 012023, 2010.06.
35. Arakawa M., Kagi H. and Fukazawa H., Laboratory measurements of infrared absorption spectra of hydrogen-ordered ice: a step to the exploration of ice XI in space, Astrophysical Journal Supplement Series, doi:10.1088/0067-0049/184/2/361, 184, 361-365, 2009.09.
36. Arakawa M., Yamamoto J. and Kagi H., Developing micro-Raman mass spectrometry for measuring carbon isotopic composition of carbon dioxide, Applied Spectroscopy, doi:10.1366/000370207781393244, 61, 701-705, 2007.07.
37. Arakawa M., Yamamoto J. and Kagi H., Micro-Raman thermometer for CO2 fluids: Temperature and density dependence on Raman spectra of CO2 fluids, Chemistry Letters, doi:10.1246/cl.2008.280, 37, 280-281, 2008.02.