Contents FRONTIERS ARTICLE 1–7 Two-dimensional silica: Crystalline and vitreous M. Heyde, S. Shaikhutdinov, H.-J. Freund Research highlights " Structural, vibrational, and electronic properties of silica films. " Monolayer, bilayer and three-dimensional silica structures. " Atomic resolution of crystalline and a vitreous silica bilayer patches. " Real space imaging of a crystal to glass transition in the silica bilayer. GASEOUS MOLECULES 8–14 New investigation on THz spectra of OH and SH radicals (X 2 Q i ) M.A. Martin-Drumel, S. Eliet, O. Pirali, M. Guinet, F. Hindle, G. Mouret, A. Cuisset Research highlights " Complementarity between broadband synchrotron-based FT-FIR and cw-THz techniques. " Pure rotational transitions of radicals within their firsts vibrational states. " Resolution of hyperfine structure of SH radical above 1 THz. " Resolution of hyperfine structure of OH radical using FT-spectroscopy. 15–18 Photoelectron spectroscopy and photochemistry of tetracyanoethylene radical anion in the gas phase Dmitry Khuseynov, Matthew T. Fontana, Andrei Sanov Research highlights " Adiabatic electron affinity of C 2 (CN) 4 (TCNE) is 3.16 ± 0.02 eV. " First direct spectroscopic determination of electron affinity of TCNE. " Photodissociation of TCNE yields CN, C 2 ðCNÞ 2 and C 2 ðCNÞ 3 . Elsevier B.V. doi:10.1016/S0009-2614(12)01121-9 Volume 550, iii–xi Contents lists available at ScienceDirect Chemical Physics Letters journal homepage: www.elsevier.com/locate/cplett
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Contents
FRONTIERS ARTICLE
1–7
Two-dimensional silica: Crystalline and vitreous
M. Heyde, S. Shaikhutdinov, H.-J. Freund
Research highlights " Structural, vibrational, and electronic properties of silica films." Monolayer, bilayer and three-dimensional silica structures. " Atomic resolution ofcrystalline and a vitreous silica bilayer patches. " Real space imaging of a crystal to glasstransition in the silica bilayer.
GASEOUS MOLECULES
8–14
New investigation on THz spectra of OH and SH radicals (X2Q
i)
M.A. Martin-Drumel, S. Eliet, O. Pirali, M. Guinet, F. Hindle,G. Mouret, A. Cuisset
Research highlights " Complementarity between broadband synchrotron-based FT-FIR andcw-THz techniques. " Pure rotational transitions of radicals within their firsts vibrationalstates. " Resolution of hyperfine structure of SH radical above 1 THz. " Resolution ofhyperfine structure of OH radical using FT-spectroscopy.
15–18
Photoelectron spectroscopy and photochemistry oftetracyanoethylene radical anion in the gas phase
Dmitry Khuseynov, Matthew T. Fontana, Andrei Sanov
Research highlights " Adiabatic electron affinity of C2(CN)4 (TCNE) is 3.16 ± 0.02 eV. " Firstdirect spectroscopic determination of electron affinity of TCNE. " Photodissociation of TCNEyields CN, C2ðCNÞ�2 and C2ðCNÞ�3 .
Elsevier B.V.doi:10.1016/S0009-2614(12)01121-9
Volume 550, iii–xi
Contents lists available at ScienceDirect
Chemical Physics Letters
journal homepage: www.elsevier .com/locate /cplet t
19–24
Kinetic simulation of the thermal degradation of phenethylphenyl ether, a model compound for the b-O-4 linkage in lignin
Ariana Beste, A.C. Buchanan III
Research highlights " Pyrolysis of phenethyl phenyl ether, a b-O-4 model compound forlignin. " Kinetic Monte Carlo based on DFT rate and equilibrium constants. " a/b-Productselectivity agrees qualitatively with experiment. " New carbon–carbon phenyl shift reactionidentified as part of the mechanism.
25–32
Electron correlation and relativistic effects in atomic structurecalculations of Th+, Th2+ ions
S.K. Roy, Rajendra Prasad, Sambhu N. Datta, P. Chandra
Research highlights " In Th+ ion, higher spin–orbit states are strongly affected bycore-valence correlation. " In Th2+ ion, the spin–orbit states are significantly influenced bycorrelation effect. " In Th2+ ion, intense transitions are from even to odd parityconfigurations at correlated level.
33–40
Silole-based oligomers as electron transport materials
Huyen Thi Nguyen, Vu Thi Thu Huong, Minh Tho Nguyen
Research highlights " Siloles have typical low-lying LUMOs. " Siloles have reorganizationenergies comparable to those of thiophenes. " Silole-based polymers could be promisingcandidates for electron transport materials.
41–46
Methane activation on Fe4 cluster: A density functional theorystudy
Qiao Sun, Zhen Li, Meng Wang, Aijun Du, Sean C. Smith
Research highlights " The study demonstrates Fe4 has strong catalytic effect on theactivation reaction of methane. " The cleavage of the first C–H bond on Fe4 is both anenergetically and dynamically favourable process. " The cluster size of iron can not onlydetermine the activity but also control the product selectivity.
Fe
Fe FeFe
CFe
Fe Fe
Fe
C
H2 + CH2-Fe4CH4+Fe4 Fe
FeFe
Fe
C
iv Contents
47–51
Low energy electron attachment to N-acetylglycine
Janina Kopyra, Constanze Kçnig-Lehmann, Eugen Illenberger
Research highlights " Electron attachment to N-acetylglycine occurs preferentially atsubexcitation energy (<3 eV). " Electron capture process is purely dissociative. " Thepredominant anion is due to the loss of a hydrogen atom resulting in the formation of (M–H)�.
HNOH
O
H3C
O
+ eH3C C+C O
O_
O
NH2
H2C
52–57
Enhanced Raman spectrum of pyrazine with the aid of resonantelectron dynamics in a nearby cluster
Research highlights " Raman spectrum of pyrazine is enhanced with the aid of electrondynamics in Na4. " Electron dynamics simulation illustrates the details of the mechanism." Specific normal modes of pyrazine couple with electronic oscillation in Na4. " The resultsshow the potential ability of cluster-enhanced Raman scattering.
58–61
Spectroscopic identification of jet-cooled 2,4-dichlorobenzylradicals generated by corona discharge
Young Wook Yoon, Chang Soon Huh, Sang Kuk Lee
Research highlights " We produce the jet-cooled 2,4-dichlorobenzyl radical by coronadischarge. " We observe the first visible vibronic emission spectra of the 2,4-dichlorobenzylradical. " We determine the spectroscopic data on the electronic transition and vibrationalmodes. " We explain substituent effect of Cl substitutions on electronic energy of the D1–D0transition. 0
20
40
60
80
19500 20000 20500 21000
Wavenumber (cm-1)
Inte
nsit
y
62–66
High resolution photoabsorption spectrum of hexafluoro-1,3-butadiene (1,3-C4F6) as studied by vacuum ultraviolet (VUV)synchrotron radiation
F. Ferreira da Silva, D. Almeida, E. Vasekova, E. Drage, N.J. Mason,P. Lim¼o-Vieira
Research highlights " Glycosidic bond cleavage with water clusters or fructose. " Energeticand structural details of proton catalytically separating difructose. " A possible autocatalysismechanism of difructose assisted by proton. " The reaction barrier is much lower thandirectly breaking a covalent bond.
73–78
Light-stimulated growth of isotropic domains in nematic liquidcrystal
M. Czajkowski, S. Bartkiewicz, J. Mysliwiec
Research highlights " Growth dynamics of photoinduced isotropic domains in azobenzenederivate is studied. " Theoretical model assuming light stimulation as main reason of thegrowth is proposed. " A population of the domains is investigated by diffraction efficiencydynamics. " Influence of parameters coming from observations is studied by series ofsimulations. " Experimental results can be precisely fitted using proposed model.
79–82
UV/Vis spectroscopy of C60 embedded in water ice
Steven H. Cuylle, Harold Linnartz, John D. Thrower
Research highlights " Broadband solid state spectroscopy. " Electronic spectrum ofC60@H2O (40 K). " Solid state signature for frozen C60 in space.
83–87
Micellar dynamics and water–water hydrogen-bonding fromtemperature-jump Monte Carlo simulations
G. Heinzelmann, W. Figueiredo, M. Girardi
Research highlights " We obtained three characteristic times for micellization. " Micellarsystems are shown to sacrifice locally the HB network. " Temperature jump simulationsrevealed water–surfactant dynamics.
vi Contents
88–93
First principles investigations of the electronic structure andchemical bonding of U3Si2C2 – A uranium silicide–carbide with therare [SiC] unit
S.F. Matar, R. Pçttgen
Research highlights " For the rare silicide–carbide U3Si2C2, experimental data are bestreproduced with GGA + U = 4 eV. " High linear incompressibility along the c-axis isidentified with Si–C alignment leading to anisotropy. " Chemical bonding is specific of theuranium sites with dominant U1–Si and U2–C. " Major Si–C bonding contributionscharacterize the compound.
94–98
Structures and lattice energies of molecular crystals using densityfunctional theory: Assessment of a local atomic potentialapproach
Research highlights " The noncovalent interactions between molecular crystals arecalculated by DFT + LAP. " The lattice parameters/energies by DFT + LAP are compared withexperimental values. " The performance of DFT + LAP is compared with DFT-D fornoncovalent interactions.
NANOSTRUCTURES AND MATERIALS
99–103
Molecular dynamics properties of varying amounts of theanticancer drug gemcitabine inside an open-ended single-walledcarbon nanotube
Research highlights " 1–6 Gemcitabine drugs confined inside SWCNT were studied usingMD simulation. " At low content, two adjacent drugs moved together due to p–p stackingformation. " At high content, the close contact of drugs promotes hydrogen bonding amongdrugs. " The drug–drug interaction is an important factor for design of releasing process.
104–110
Gate-voltage-dependent Landau levels in AA-stacked bilayergraphene
Sing-Jyun Tsai, Yu-Huang Chiu, Yen-Hung Ho, Ming-Fa Lin
Research highlights " We study the Landau levels of bilayer graphene in gate voltages by thePeierls tight-binding model. " The gate voltage strongly influences the Landau level spectra." There exist semiconductor–semimetal transitions at certain gate voltages. " Somecarriers are transferred between different layers.
Contents vii
111–117
Cooperative behavior in functionalized graphene: Explaining theoccurrence of 1,3 cycloaddition of azomethine ylides ontographene
Pablo A. Denis, Federico Iribarne
Research highlights " Cooperative behavior is responsible for the occurrence of 1,3 dipolarcycloadditions and other organic reactions. " Reaction energies are increased up to 30 kcal/mol per functional group. " Functionalization forming infinite armchair lines is the avenueto heavily functionalize graphene. " The band gap can be varied from 0 to 2 eV!.
118–124
Role of lone pair and p-orbital interaction in formation of waternanostructures confined in carbon nanotubes
Research highlights " Confined water in carbon nanotubes. " ‘Water-chains’, ‘water-cluster’and ‘water-tube’ like nanostructures. " Pristine and functionalized carbon nanotubes." H-bonding, lone-pair and p-orbital interaction play a major role.
125–129
Nanofibrous-like ZnO layers deposited by magnetron sputteringand their integration in dye-sensitized solar cells
O. Lupan, V.M. Gu�rin, L. Ghimpu, I.M. Tiginyanu, T. Pauport�
Research highlights " Preparation by magnetron sputtering of ZnO nanofiber network asthick layers. " High optical and structural quality of the material. " Good electricalcontinuity and connection to the substrate. " High short circuit current dye-sensitized solarcells.
130–133
Layer number-dependent structural evolution oftwo-dimensional diamond films
Hongdong Li, Jia Li, Zhigang Wang, Guangtian Zou
Research highlights " The two dimensional (2D) diamond films were calculated by the firstprinciples calculations. " The structural evolutions and electrical properties of 2D diamondare dependent on layer number. " The 2D thinnest diamond film and gradient-graphite-diamond-like structures have been predicted.
viii Contents
134–137
Spin orbital effect in lanthanides doped silicon cage clusters
Lingju Guo, Xiaohong Zheng, Z. Zeng, Chao Zhang
Research highlights " Cage-like Si16 clusters can be stabilized by doping Ln atoms." Fullerene-like LnSi16 structures are always stable than Frank–Kasper structures. " Someof the LnSi16 clusters maintain large total magnetic moments. " The clusters with Pr, Nd, Smand Tm have large orbital moments. " The directions of orbital moments and spin momentsmatches the Hund’s 3rd rule.
138–145
Single molecule spectroscopic studies of organic rectifierscomposed of pyrene and perylenebisimide
Debra Jo Scardino, Rajesh Kota, Daniell L. Mattern,Nathan I. Hammer
Research highlights " Molecular rectifier properties vary at the single molecule level." The presence of pyrene affects perylenebisimide’s fluorescence stability. " Embedding inpolymer thin film stabilizes perylenebisimide’s fluorescence. " Unique dipole emissionpatterns reveal molecular orientation in polymer thin film. " Pyrene acts as a structuredirecting group for the orientation of perylene within the polymer thin films.
146–149
Supersonic quasi-particles dynamics in organic semiconductors
Marcus Vin�cius Alves da Silva, Pedro Henrique de Oliveira Neto,Wiliam Ferreira da Cunha, Ricardo Gargano,Geraldo Magela e Silva
Research highlights " Quasi-particles behavior in organic semiconductors is investigated." Dynamic study for several external electric fields and impurities. " Transition fromsubsonic to supersonic regime was determined. " Useful information about the conductivityof polymers were obtained.
BIOMOLECULES
150–155
The cis influence of the corrin in vitamin B12 models
Penny P. Govender, Isabelle Navizet, Christopher B. Perry,Helder M. Marques
Research highlights " DFT calculations explore the cis influence of corrins on Co–CH3 bondhomolysis. " There is normal trans influence between Co–CH3 and Co–NH3 bond lengths." Increasing electron donation from the corrin causes the Co–CH3 BDE to decrease." Differences in BDE arises from differential stabilization between 6C–Co(III) and5(C)–Co(II).
Contents ix
NEW EXPERIMENTAL OR THEORETICAL METHODS
156–161
Phase-cycling schemes for pump–probe beam geometrytwo-dimensional electronic spectroscopy
Zhengyang Zhang, Kym Lewis Wells,Edward William James Hyland, Howe-Siang Tan
Research highlights " Theoretical explanation and Experimental demonstration of phasecycling schemes for 2D pump probe spectroscopy. " 1 � 2 Phase cycling recovers bothrephasing and nonrephasing 2D spectra under certain experimental situations. " 1 � 3Phase cycling recovers all 2D spectra that has been shown hitherto to be only obtained with a1 � 4 phase cycling scheme. " Experimental studies performed with excellent agreementwith theory.
162–169
Short range DFT combined with long-range local RPA within arange-separated hybrid DFT framework
E. Chermak, B. Mussard, J.G. �ngy�n, P. Reinhardt
Research highlights " Monomer correlation energies not needed in local orbitals and thedispersion approach. " Dispersion approximation valid in range-separated DFT even forhydrogen bonded complexes. " Selection of contributions to the RPA correlation part viamono-excitations useful. " Singles-CI orbital optimization can be formulated and usedadvantageously in DFT.
170–174
Double effects of high pressure and Sb doping content onthermoelectric properties of Bi2Te3-based alloys
Xin Guo, Xiaopeng Jia, Taichao Su, Kaikai Jie, Hairui Sun,Hongan Ma
Research highlights " We research the thermoelectric properties of Bi2Te3-based withdouble variables. " Bi2�xSbxTe3 is synthesized by a new method of high pressure and hightemperature. " We present an optimal carrier concentration range (3.4 � 1019–3.8 � 1019 cm�3). " The power factor can be enhanced if carrier concentration is in thisrange.
175–180
Theoretical and experimental study on narrowing the band gapof carbon nitride photocatalyst by coupling a wide gap molecule
Research highlights " Wide gap anhydride can sensitize wide band gap carbon nitridepolymer (CNP). " Sensitization is realized using LUMO of anhydride to accept electrons of VBin CNP. " The interaction between anhydride and CNP also influences VB and CB energies ofCNP.
x Contents
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