Ultrafast Spectroscopic Signatures of Coherent Electron-Transfer Mechanisms in a Transition Metal Complex

The prevalence of ultrafast electron-transfer processes in light-harvesting materials has motivated a deeper understanding of coherent reaction mechanisms. Kinetic models based on the traditional (equilibrium) form of Fermi's Golden Rule are commonly employed to understand photoinduced electron-transfer dynamics. These models fail in two ways when the electron-transfer process is fast compared to solvation dynamics and vibrational dephasing. First, electron-transfer dynamics may be accelerated if the photoexcited wavepacket traverses the point of degeneracy between donor and acceptor states in the solvent coordinate. Second, traditional kinetic models fail to describe electron-transfer transitions that yield products which undergo coherent nuclear motions. We address the second point in this work. Transient absorption spectroscopy and a numerical model are used to investigate coherent back-electron-transfer mechanisms in a transition metal complex composed of titanium and catechol, [Ti(cat)3]2-. The transient absorption experiments reveal coherent wavepacket motions initiated by the back-electron-transfer process. Model calculations suggest that the vibrationally coherent product states may originate in either vibrational populations or coherences of the reactant. That is, vibrational coherence may be produced even if the reactant does not undergo coherent nuclear motions. The analysis raises a question of broader significance: can a vibrational population-to-coherence transition (i.e., a nonsecular transition) accelerate electron-transfer reactions even when the rate is slower than vibrational dephasing

Communication: Uncovering correlated vibrational cooling and electron transfer dynamics with multidimensional spectroscopy

Analogues of 2D photon echo methods in which two population times are sampled have recently been used to expose heterogeneity in chemical kinetics. In this work, the two population times sampled for a transition metal complex are transformed into a 2D rate spectrum using the maximum entropy method. The 2D rate spectrum suggests heterogeneity in the vibrational cooling (VC) rate within the ensemble. In addition, a cross peak associated with VC and back electron transfer (BET) dynamics reveals correlation between the two processes. We hypothesize that an increase in the strength of solute-solvent interactions, which accelerates VC, drives the system toward the activationless regime of BET

Resolving rotational stacking disorder and electronic level alignment in a 2d oligothiophene-based lead iodide perovskite

Two-dimensional (2D) hybrid organic-inorganic perovskites (HOIPs) represent diverse quantum well heterostructures composed of alternating inorganic and organic layers. While 2D HOIPs are nominally periodic in three dimensions for X-ray scattering, the inorganic layers can orient quasi-randomly, leading to rotational stacking disorder (RSD). RSD manifests as poorly resolved, diffuse X-ray scattering along the stacking direction, limiting the structural description to an apparently disordered subcell. However, local ordering preferences can still exist between adjacent unit cells and can considerably impact the properties, particularly the electronic structure. Here, we elucidate RSD and determine the preferred local ordering in the 2D [AE2T]PbI4 HOIP (AE2T: 5,5′-bis(ethylammonium)-[2,2′-bithiophene]). We use first-principles calculations to determine energy differences between a set of systematically generated supercells with different order patterns. We show that interlayer ordering tendencies are weak, explaining the observed RSD in terms of differing in-plane rotation of PbI6 octahedra in neighboring inorganic planes. In contrast, the ordering preference within a given organic layer is strong, favoring a herringbone-type arrangement of adjacent AE2T cations. The calculated electronic level alignments of proximal organic and inorganic frontier orbitals in the valence band vary significantly with the local arrangement of AE2T cations; only the most stable AE2T configuration leads to an interfacial type-Ib band alignment consistent with observed optical properties. The present study underscores the importance of resolving local structure arrangements in 2D HOIPs for reliable structure-property prediction

Direct-Bandgap 2D Silver-Bismuth Iodide Double Perovskite: The Structure-Directing Influence of an Oligothiophene Spacer Cation

Three-dimensional (3D) hybrid organic-inorganic lead halide perovskites (HOIPs) feature remarkable optoelectronic properties for solar energy conversion but suffer from long-standing issues of environmental stability and lead toxicity. Associated two-dimensional (2D) analogues are garnering increasing interest due to superior chemical stability, structural diversity, and broader property tunability. Toward lead-free 2D HOIPs, double perovskites (DPs) with mixed-valent dual metals are attractive. Translation of mixed-metal DPs to iodides, with their prospectively lower bandgaps, represents an important target for semiconducting halide perovskites, but has so far proven inaccessible using traditional spacer cations due to either intrinsic instability or formation of competing non-perovskite phases. Here, we demonstrate the first example of a 2D Ag-Bi iodide DP with a direct bandgap of 2.00(2) eV, templated by a layer of bifunctionalized oligothiophene cations, i.e., (bis-aminoethyl)bithiophene, through a collective influence of aromatic interactions, hydrogen bonding, bidentate tethering, and structural rigidity. Hybrid density functional theory calculations for the new material reveal a direct bandgap, consistent with the experimental value, and relatively flat band edges derived principally from Ag-d/I-p (valence band) and Bi-p/I-p (conduction band) states. This work opens up new avenues for exploring specifically designed organic cations to stabilize otherwise inaccessible 2D HOIPs with potential applications for optoelectronics

Search for the standard model Higgs boson decaying into two photons in pp collisions at sqrt(s)=7 TeV

A search for a Higgs boson decaying into two photons is described. The analysis is performed using a dataset recorded by the CMS experiment at the LHC from pp collisions at a centre-of-mass energy of 7 TeV, which corresponds to an integrated luminosity of 4.8 inverse femtobarns. Limits are set on the cross section of the standard model Higgs boson decaying to two photons. The expected exclusion limit at 95% confidence level is between 1.4 and 2.4 times the standard model cross section in the mass range between 110 and 150 GeV. The analysis of the data excludes, at 95% confidence level, the standard model Higgs boson decaying into two photons in the mass range 128 to 132 GeV. The largest excess of events above the expected standard model background is observed for a Higgs boson mass hypothesis of 124 GeV with a local significance of 3.1 sigma. The global significance of observing an excess with a local significance greater than 3.1 sigma anywhere in the search range 110-150 GeV is estimated to be 1.8 sigma. More data are required to ascertain the origin of this excess.Comment: Submitted to Physics Letters

Measurement of isolated photon production in pp and PbPb collisions at sqrt(sNN) = 2.76 TeV

Isolated photon production is measured in proton-proton and lead-lead collisions at nucleon-nucleon centre-of-mass energies of 2.76 TeV in the pseudorapidity range |eta|<1.44 and transverse energies ET between 20 and 80 GeV with the CMS detector at the LHC. The measured ET spectra are found to be in good agreement with next-to-leading-order perturbative QCD predictions. The ratio of PbPb to pp isolated photon ET-differential yields, scaled by the number of incoherent nucleon-nucleon collisions, is consistent with unity for all PbPb reaction centralities.Comment: Submitted to Physics Letters

Search for a W ' boson decaying to a muon and a neutrino in pp collisions at √s =7 TeV

This is the Pre-Print version of the Article. The official published version can be accessed from the link below - Copyright @ 2011 ElsevierA new heavy gauge boson, W', decaying to a muon and a neutrino, is searched for in pp collisions at a centre-of-mass of 7 TeV. The data, collected with the CMS detector at the LHC, correspond to an integrated luminosity of 36 inverse picobarns. No significant excess of events above the standard model expectation is found in the transverse mass distribution of the muon-neutrino system. Masses below 1.40 TeV are excluded at the 95% confidence level for a sequential standard-model-like W'. The W' mass lower limit increases to 1.58 TeV when the present analysis is combined with the CMS result for the electron channel.This work is supported by the FMSR (Austria); FNRS and FWO (Belgium); CNPq, CAPES, FAPERJ, and FAPESP (Brazil); MES (Bulgaria); CERN; CAS, MoST, and NSFC (China); COLCIENCIAS (Colombia); MSES (Croatia); RPF (Cyprus); Academy of Sciences and NICPB (Estonia); Academy of Finland, ME, and HIP (Finland); CEA and CNRS/IN2P3 (France); BMBF, DFG, and HGF (Germany); GSRT (Greece); OTKA and NKTH (Hungary); DAE and DST (India); IPM (Iran); SFI (Ireland); INFN (Italy); NRF and WCU (Korea); LAS (Lithuania); CINVESTAV, CONACYT, SEP, and UASLP-FAI (Mexico); PAEC (Pakistan); SCSR (Poland); FCT (Portugal); JINR (Armenia, Belarus, Georgia, Ukraine, Uzbekistan); MST and MAE (Russia); MSTD (Serbia); MICINN and CPAN (Spain); Swiss Funding Agencies (Switzerland); NSC (Taipei); TUBITAK and TAEK (Turkey); STFC (United Kingdom); DOE and NSF (USA)

Observation of a new Xi(b) baryon

The first observation of a new b baryon via its strong decay into Xi(b)^- pi^+ (plus charge conjugates) is reported. The measurement uses a data sample of pp collisions at sqrt(s) = 7 TeV collected by the CMS experiment at the LHC, corresponding to an integrated luminosity of 5.3 inverse femtobarns. The known Xi(b)^- baryon is reconstructed via the decay chain Xi(b)^- to J/psi Xi^- to mu^+ mu^- Lambda^0 pi^-, with Lambda^0 to p pi^-. A peak is observed in the distribution of the difference between the mass of the Xi(b)^- pi^+ system and the sum of the masses of the Xi(b)^- and pi^+, with a significance exceeding five standard deviations. The mass difference of the peak is 14.84 +/- 0.74 (stat.) +/- 0.28 (syst.) MeV. The new state most likely corresponds to the J^P=3/2^+ companion of the Xi(b).Comment: Submitted to Physical Review Letter

Measurement of the charge ratio of atmospheric muons with the CMS detector

This is the pre-print version of this Article. The official published version can be accessed from the link below - Copyright @ 2010 ElsevierWe present a measurement of the ratio of positive to negative muon fluxes from cosmic ray interactions in the atmosphere, using data collected by the CMS detector both at ground level and in the underground experimental cavern at the CERN LHC. Muons were detected in the momentum range from 5 GeV/c to 1 TeV/c. The surface flux ratio is measured to be 1.2766 \pm 0.0032(stat.) \pm 0.0032 (syst.), independent of the muon momentum, below 100 GeV/c. This is the most precise measurement to date. At higher momenta the data are consistent with an increase of the charge ratio, in agreement with cosmic ray shower models and compatible with previous measurements by deep-underground experiments

Measurements of inclusive W and Z cross sections in pp collisions at root s=7 TeV

This is the pre-print version of the Published Article, which can be accessed from the link below - Copyright @ 2011 Springer VerlagMeasurements of inclusive W and Z boson production cross sections in pp collisions at sqrt(s)=7 TeV are presented, based on 2.9 inverse picobarns of data recorded by the CMS detector at the LHC. The measurements, performed in the electron and muon decay channels, are combined to give sigma(pp to WX) times B(W to muon or electron + neutrino) = 9.95 \pm 0.07(stat.) \pm 0.28(syst.) \pm 1.09(lumi.) nb and sigma(pp to ZX) times B(Z to oppositely charged muon or electron pairs) = 0.931 \pm 0.026(stat.) \pm 0.023(syst.) \pm 0.102(lumi.) nb. Theoretical predictions, calculated at the next-to-next-to-leading order in QCD using recent parton distribution functions, are in agreement with the measured cross sections. Ratios of cross sections, which incur an experimental systematic uncertainty of less than 4%, are also reported