Archive for the ‘Hot Article’ Category

‘HOT’ PCCP paper: isolated molecules cooled in a supersonic expansion

The electronic and vibrational properties of diphenyldiacetylene and diphenylvinylacetylene are characterized under jet-cooled conditions.

Laser induced fluorescence (LIF) excitation scans and dispersed fluorescence (DFL) spectra have been recorded for two four-carbon α,ω-diphenyl systems, diphenyldiacetylene (DPDA) and trans-diphenylvinylacetylene (DPVA) as isolated molecules cooled in a supersonic expansion.

The excited states and vibronic spectroscopy of diphenyldiacetylene and diphenylvinylacetylene
Joshua A. Sebree and Timothy S. Zwier
Phys. Chem. Chem. Phys., 2012, DOI: 10.1039/C1CP22857A

orbitals

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Editor’s Choice: Theoretical and Computational Chemistry

journal cover  imagePhysical Chemistry Chemical Physics (PCCP) Advisory Board members Stefan Grimme, Dage Sundholm and So Hirata, experts in the field of theoretical and computational chemistry, have picked their favourite articles recently published in this area in PCCP. This collection highlights the breadth of theoretical research featured in PCCP.

Theory is an important part of PCCP, which is supported by the theoretical and computational chemists on our Editorial and Advisory Boards. In addition to Professors Grimme, Sundholm and Hirata, these include Carlo Adamo, Vincenzo Barone, Matthais Bickelhaupt, David Clary, Alain Fuchs, Peter Gill, Martin Head-Gordon, Pavel Hobza, Roman Krems, Todd Martinez, Pekka Pyykkö, Joachim Sauer, Berend Smit and Hans-Joachim Werner.

Read our Editor’s choice ‘theory’ selection for free today:

New electron correlation theories for transition metal chemistry
Konrad H. Marti and Markus Reiher
DOI: 10.1039/C0CP01883J

High-dimensional ab initio potential energy surfaces for reaction dynamics calculations
Joel M. Bowman, Gábor Czakó and Bina Fu
DOI: 10.1039/C0CP02722G

Forward–backward semiclassical and quantum trajectory methods for time correlation functions
Nancy Makri
DOI: 10.1039/C0CP02374D

Electronic structure in real time: mapping valence electron rearrangements during chemical reactions
Philippe Wernet
DOI: 10.1039/C0CP02934C

The polymorphism of ice: five unresolved questions
Christoph G. Salzmann, Paolo G. Radaelli, Ben Slater and John L. Finney
DOI: 10.1039/C1CP21712G

Relativity and the mercury battery
Patryk Zaleski-Ejgierd and Pekka Pyykkö
DOI: 10.1039/C1CP21738K

Aromaticity of strongly bent benzene rings: persistence of a diatropic ring current and its shielding cone in [5]paracyclophane
Leonardus W. Jenneskens, Remco W. A. Havenith, Alessandro Soncini and Patrick W. Fowler
DOI: 10.1039/C1CP21950B

Ab initio molecular dynamics simulations of a binary system of ionic liquids
Marc Brüssel, Martin Brehm, Thomas Voigt and Barbara Kirchner
DOI: 10.1039/C1CP21550G

On the physisorption of water on graphene: a CCSD(T) study
Elena Voloshina, Denis Usvyat, Martin Schütz, Yuriy Dedkov and Beate Paulus
DOI: 10.1039/C1CP20609E

A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions
Lars Goerigk and Stefan Grimme
DOI: 10.1039/C0CP02984J

Interlayer interaction and relative vibrations of bilayer graphene
Irina V. Lebedeva, Andrey A. Knizhnik, Andrey M. Popov, Yurii E. Lozovik and Boris V. Potapkin
DOI: 10.1039/C0CP02614J

Demystifying the solvatochromic reversal in Brooker’s merocyanine dye
N. Arul Murugan, Jacob Kongsted, Zilvinas Rinkevicius and Hans Ågren
DOI: 10.1039/C0CP01014F

Microscopic structure and dynamics of air/water interface by computer simulations—comparison with sum-frequency generation experiments
Yanting Wang, Nathan O. Hodas, Yousung Jung and R. A. Marcus
DOI: 10.1039/C0CP02745F

Pseudo Jahn–Teller origin of cistrans and other conformational changes. The role of double bonds
Pablo Garcia-Fernandez, Yang Liu, Isaac B. Bersuker and James E. Boggs
DOI: 10.1039/C0CP00900H

Intracule functional models. V. Recurrence relations for two-electron integrals in position and momentum space
Joshua W. Hollett and Peter M. W. Gill
DOI: 10.1039/C0CP02154G

Potential energy surfaces for gas-surface reactions
Terry J. Frankcombe and Michael A. Collins
DOI: 10.1039/C0CP01843K

Temperature dependence of crystal growth of hexagonal ice (Ih)
Dmitri Rozmanov and Peter G. Kusalik
DOI: 10.1039/C1CP21210A

A molecular dynamics study of 1,1-diamino-2,2-dinitroethylene (FOX-7) crystal using a symmetry adapted perturbation theory-based intermolecular force field
DeCarlos E. Taylor, Fazle Rob, Betsy M. Rice, Rafal Podeszwa and Krzysztof Szalewicz
DOI: 10.1039/C1CP21342C

Are ab initio quantum chemistry methods able to predict vibrational states up to the dissociation limit for multi-electron molecules close to spectroscopic accuracy?
Péter G. Szalay, Filip Holka, Julien Fremont, Michael Rey, Kirk A. Peterson and Vladimir G. Tyuterev
DOI: 10.1039/C0CP01334J

Computing the inhomogeneous broadening of electronic transitions in solution: a first-principle quantum mechanical approach
Francisco José Avila Ferrer, Roberto Improta, Fabrizio Santoro and Vincenzo Barone
DOI: 10.1039/C1CP22115A

First-principles calculation of electronic spectra of light-harvesting complex II
Carolin König and Johannes Neugebauer
DOI: 10.1039/C0CP02808H

Beyond the Förster formulation for resonance energy transfer: the role of dark states
C. Sissa, A. K. Manna, F. Terenziani, A. Painelli and S. K. Pati
DOI: 10.1039/C1CP21004A

Publishing work of the highest quality in the broad fields of physical chemistry, chemical physics and biophysical chemistry, PCCP is the ideal place to publish your research.

On behalf of the Editorial Board we invite you to submit your best work to PCCP.

PCCP now offers you the chance to publish your accepted article as an Accepted Manuscript. This means that your research is available, in citable form, to the community even more rapidly. Click here for more information.

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Microbial fuel cell uses urine to produce energy

Urine-powered fuel cells could generate electricity and reclaim essential nutrients directly from human and animal waste, say UK scientists. The development could make wastewater treatment easier and cheaper, and provide an abundant source of locally generated power.

The team, led by Ioannis Ieropolous and John Greenman at the Bristol Robotics Laboratory, developed microbial fuel cells (MFCs) – which use bacteria to break down organic molecules and generate electricity – that could run on the organic molecules found in urine, such as uric acid, creatinine and small peptides. 

Finding the right bacteria to munch these molecules was relatively easy – wastewater treatment plants routinely employ bacteria to do the job. But the crucial point, says Ieropoulos, is that the current processes are energy intensive, whereas the fuel cell approach could turn it into an energy-generating process. Getting the urine on the other hand, required a volunteer. ‘It’s one of us,’ quips Greenman, ‘but we’re not going to say which one.’

The bacteria form a robust biofilm on the anode surface of the fuel cell, and pass electrons to the electrode as they respire and metabolise the fuel molecules in the urine. The team have found that smaller cells have higher energy densities, ‘so we’ve followed a path of miniaturisation and multiplication, building stacks of cells,’ says Ieropoulos. An individual cell can produce a current of 0.25mA for 3 days from 25ml of urine, so stacks of hundreds or thousands of cells could run on the amounts of urine available from homes, farms, or public toilets, for example. ‘Initially we’d probably be targeting local microgeneration,’ says Greenman.

Urine fuel cell

The microbial fuel cell metabolises organic compounds in urine to produce electricity

The lack of solids – which could clog up the fuel cells – in urine compared to more general wastewater gives this system a significant advantage, comments Lars Angenent, director of the agricultural waste management lab at Cornell University in Ithaca, US. But, he points out, there are some issues: ‘Firstly, there is a societal question – do people want to separate their urine?’ Although there are modern toilets that can perform the separation, it would require a social change. ‘Then there is the cost issue – they’ve shown it can be done, but will it be economical?’

Angenent observes that some research has moved from fuel cells towards electrolysis of the urea in wastewater to form hydrogen or hydrogen peroxide. These valuable products help balance the device costs. However, as Ieropolous explains, the bacteria in their fuel cell can’t metabolise urea as fuel, so it could be possible to pass the urine first through an electrolytic cell to generate hydrogen, then through the MFC to generate electricity from the other organics.

As well as generating power, the team’s MFCs could help reclaim essential nutrients from waste, adds Greenman. Urine is particularly troublesome in wastewater treatment, since it not only contains organic compounds, but also high levels of nitrogen, phosphorus and potassium. Treatment plants currently expend significant effort and energy removing these elements from wastewater, as releasing them constitutes environmental pollution in the same way as excess fertiliser leaching from agricultural land – it promotes algal blooms that can choke out rivers and waterways.

The fuel cell bacteria could sequester those salts to grow and divide, but in normal urine the balance of nutrients is wrong – there isn’t enough carbon fuel for them to grow fast enough to take up sufficient amounts of the other elements. ‘But if you balance it by adding a cheap carbon source like acetate,’ says Greenman, ‘all the nitrogen, phosphate and potassium is captured into daughter bacteria, which perfuse out of the MFC and can be filtered out and dug back into the ground as fertiliser.’

Phillip Broadwith

Read the paper from Physical Chemistry Chemical Physics:

Urine utilisation by Microbial Fuel Cells; energy fuel for the future
Ioannis Ieropoulos, John Greenman and Chris Melhuish
Phys. Chem. Chem. Phys., 2011
DOI: 10.1039/c1cp23213d

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Editor’s Choice: Nanoscale Chemistry

Journal coverPhysical Chemistry Chemical Physics (PCCP) Advisory Board member Professor Paul Mulvaney, an expert in the field of nanoscale chemistry, has picked his favourite articles recently published in this area in PCCP.
Read Professor Mulvaney’s Editor’s choice selection, along with his comments on each article, for free today:

A timely review of the rapidly developing field of a nanocrystal self-assembly. This perspective discusses the new techniques emerging and the exciting new materials created. The focus is on thiol derivatized gold particles but will be of interest to anyone interested in nanocrystal assembly:

Functional noble metal nanoparticle superlattices grown at interfaces
Keisaku Kimura and Thalappil Pradeep
DOI: 10.1039/C1CP22279A

A review of electron transfer dynamics of nanoparticle-modified electrodes. This review certainly suggests wet-chemical electronics is coming of age:

Electrochemical charge transfer mediated by metal nanoparticles and quantum dots
Gabriela P. Kissling, David O. Miles and David J. Fermín
DOI: 10.1039/C1CP21996K

An in-depth review of the controversy surrounding the detection and measurement difficulties associated with multi-exciton generation. The article suggests some novel ways forward:

Multiple exciton generation in nanocrystal quantum dots – controversy, current status and future prospects
David J. Binks
DOI: 10.1039/C1CP20225A

An exciting review by leading researchers of the issues involving energy relaxation during NC–NC interactions:

Energetics and dynamics of exciton–exciton interactions in compound colloidal semiconductor quantum dots
Zvicka Deutsch, Assaf Avidan, Iddo Pinkas and Dan Oron
DOI: 10.1039/C0CP02253E

Catalysis is one of the outstanding areas in physical chemistry where empirical breakthroughs lead theory and understanding. This review tries to capture the main trends in the application and design of nano crystals in catalysis. A good read for those who think catalysis can’t be tackled rationally:

Colloidal metal nanoparticles as a component of designed catalyst
Chun-Jiang Jia and Ferdi Schüth
DOI: 10.1039/C0CP02680H

An interesting paper, which finds further evidence for multi-exciton generation in PbS:

Electronic and surface properties of PbS nanoparticles exhibiting efficient multiple exciton generation
Samantha J. O. Hardman, Darren M. Graham, Stuart K. Stubbs, Ben F. Spencer, Elaine A. Seddon, Ho-Ting Fung, Sandra Gardonio, Fausto Sirotti, Mathieu G. Silly, Javeed Akhtar, Paul O’Brien, David J. Binks and Wendy R. Flavell
DOI: 10.1039/C1CP22330E

Freund and colleagues demonstrate size dependent binding of CO to Pd. Given the importance of CO removal as a pollutant, this is a particularly exciting piece of work that also shows systematic understanding of “nanoscale” effects in catalysis is possible:

Adsorption energetics of CO on supported Pd nanoparticles as a function of particle size by single crystal microcalorimetry
J. M. Flores-Camacho, J.-H. Fischer-Wolfarth, M. Peter, C. T. Campbell, S. Schauermann and H.-J. Freund
DOI: 10.1039/C1CP21677E

Cationic surfactants normally present in these rods makes their use cumbersome. Hu and Gao show that the use of amphiphilic coatings helps gold nanorods to work efficiently:

Multilayer coating of gold nanorods for combined stability and biocompatibility
Xiaoge Hu and Xiaohu Gao
DOI: 10.1039/C0CP02434A

The authors show that interactions between nanocrystals affects the tunneling current between an STM tip and the NCs:

Controlled electrostatic assembly of quantum dots vis-à-vis their electronic coupling and transport gap
Batu Ghosh and Amlan J. Pal
DOI: 10.1039/C0CP02729D

This paper shows that a single nanoparticle can be detected when it is driven through a nanopore electrophoretically. Particularly interesting is the role of the double layer around not just the pore but also the particle in determining the sensitivity of this process:

Electrokinetic particle translocation through a nanopore
Ye Ai and Shizhi Qian
DOI: 10.1039/C0CP02267E

Publishing work of the highest quality in the broad fields of physical chemistry, chemical physics and biophysical chemistry, PCCP is the ideal place to publish your research.

On behalf of the Editorial board we invite you to submit your best work to PCCP.

PCCP now offers you the chance to publish your accepted article as an Accepted Manuscript. This means that your research is available, in citable form, to the community even more rapidly. Click here to find out more.

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Nanorods in just one minute

Scientists in China and the UK have made tungsten oxide (WO3) nanorods using an electron beam in one minute.

The WO3 was treated with an amine “molecular knife” that cut the particles under the beam’s irradiation.

Previous ways of making these nanorods have involved harsh conditions, high reaction temperatures and elaborate routes. The rods can be used in catalysis, writing-reading-erasing memory devices and as a negative electrode in lithium ion batteries, say the researchers.

Read the ‘hot’ PCCP paper today:

Accelerated electron beam induced breakdown of commercial WO3 into nanorods in the presence of triethylamine
G Dawson, W Zhou and R Blackley
Phys. Chem. Chem. Phys., 2011, DOI: 10.1039/c1cp22596k

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Gold: Faraday Discussion 152 now published!

Gold front coverFaraday Discussion 152: Gold has now  been published online.

Take a look at this exciting volume which covers the following themes:

  • Gold catalysis at the gas solid interface
  • Gold catalysis and materials science
  • Theoretical insights on gold catalysis
  • Gold catalysis and enhanced selectivity

In the volume you can find all the papers and exciting discussion from the conference held in Cardiff, UK, in July. These are just some of the highlights:

Role of perimeter interfaces in catalysis by gold nanoparticles
Masatake Haruta
DOI: 10.1039/C1FD00107H

A periodic DFT study of the activation of O2 by Au nanoparticles on α-Fe2O3
Kara L. Howard and David J. Willock
DOI: 10.1039/C1FD00026H

A paradigm for predicting selective oxidation on noble metals: oxidative catalytic coupling of amines and aldehydes on metallic gold
Bingjun Xu, Cynthia M. Friend and Robert J. Madix
DOI: 10.1039/C1FD00012H

Oxidative coupling of alcohols on gold: Insights from experiments and theory
Bingjun Xu and Cynthia M. Friend
DOI: 10.1039/C1FD00015B

You can purchase this volume as an individual book through our website.

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PCCP Perspective: Tailored heterogenous catalysis using colloidal nanoparticles

Colloidal nanoparticles capped with organic ligands can be used to catalyze reactions in the gas phase. Their various advantages include size and morphology control as well as enhanced stability and protection of the catalyst compared to uncapped nanoparticles.

Sonström and Bäumer describe the state of the art in this exciting research area and give their perspective on its future challenges and opportunities.

Read their PCCP Perspective now:

Supported colloidal nanoparticles in heterogeneous gas phase catalysis: on the way to tailored catalysts
P. Sonström and M. Bäumer
Phys. Chem. Chem. Phys., 2011
DOI: 10.1039/C1CP22048A

Image

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Editor’s Choice: Excited states, proton and electron transfer

journal cover imagePhysical Chemistry Chemical Physics (PCCP) Advisory Board member Professor Carlo Adamo, an expert in the fields of excited states, proton and electron transfer, has picked his favourite articles recently published in this area in PCCP.

Read Professor Adamo’s Editor’s choice selection for free today:

Quantum coherence and its interplay with protein environments in photosynthetic electronic energy transfer
Akihito Ishizaki, Tessa R. Calhoun, Gabriela S. Schlau-Cohen and Graham R. Fleming
DOI: 10.1039/C003389H

Energetics and dynamics of proton transfer reactions along short water wires
Ville R. I. Kaila and Gerhard Hummer
DOI: 10.1039/C1CP21112A

Multiscale modelling of mesoscopic phenomena triggered by quantum events: light-driven azo-materials and beyond
Marcus Böckmann, Dominik Marx, Christine Peter, Luigi Delle Site, Kurt Kremer and Nikos L. Doltsinis
DOI: 10.1039/C0CP01661F

Combined effect of stacking and solvation on the spontaneous mutation in DNA
José P. Cerón-Carrasco, José Zúñiga, Alberto Requena, Eric A. Perpète, Catherine Michaux and Denis Jacquemin
DOI: 10.1039/C1CP20946A

QM/MM studies of structural and energetic properties of the far-red fluorescent protein HcRed
Qiao Sun, Markus Doerr, Zhen Li, Sean C. Smith and Walter Thiel
DOI: 10.1039/B918523B

Effect of solvent and additives on the open-circuit voltage of ZnO-based dye-sensitized solar cells: a combined theoretical and experimental study
Tangui Le Bahers, Frédéric Labat, Thierry Pauporté and Ilaria Ciofini
DOI: 10.1039/C004358C

Theoretical study of the opsin shift of deprotonated retinal schiff base in the M state of bacteriorhodopsin
Kazuhiro J. Fujimoto, Kota Asai and Jun-ya Hasegawa
DOI: 10.1039/C0CP00361A

Multiscale quantum mechanics/electromagnetics simulation for electronic devices
ChiYung Yam, Lingyi Meng, GuanHua Chen, Quan Chen and Ngai Wong
DOI: 10.1039/C1CP20766K

Fluorescence spectra of organic dyes in solution: a time dependent multilevel approach
Vincenzo Barone, Julien Bloino, Susanna Monti, Alfonso Pedone and Giacomo Prampolini
DOI: 10.1039/C0CP01320J

Insights on the mechanism of proton transfer reactions in amino acids
Fernanda Duarte, Esteban Vöhringer-Martinez and Alejandro Toro-Labbé
DOI: 10.1039/C0CP02076A

Publishing work of the highest quality in the broad fields of physical chemistry, chemical physics and biophysical chemistry, PCCP is the ideal place to publish your research.

On behalf of the Editorial Board we invite you to submit your best work to PCCP.

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Dissolving salt is more complex than you might think

Michaelides et al. have investigated how NaCl dissolves in water using ab initio modelling of the system. The process involves several steps and begins with the loss of Cl ions. An improved understanding of the dissolution process of salt could be applied to many environmental and atmospheric chemistry problems.

This interesting research is also highlighted on the website of University College London’s Chemistry Department.

Read the full communication:

Initial stages of salt crystal dissolution determined with ab initio molecular dynamics
Li-Min Liu, Alessandro Laio and Angelos Michaelides
Phys. Chem. Chem. Phys., 2011, 13, 13162-13166
DOI: 10.1039/C1CP21077G

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3D graphene structures are potential gas separation membranes

HOT PCCP Communication

A 3D network structure made of graphene planes with carbon nanotube pillars has been modeled by Polish scientists. These materials show great promise for application as gas separation membranes.

Read the full article:

Pillared graphene as a gas separation membrane
Radosław P. Wesołowski and Artur P. Terzyk
DOI: 10.1039/C1CP21590F

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