Femtosecond pulsed lasers have been widely used over the past decades due to their capability to fabricate precise patterns at the micro-and nano-lengths scales. A key issue for efficient material processing is the de...Femtosecond pulsed lasers have been widely used over the past decades due to their capability to fabricate precise patterns at the micro-and nano-lengths scales. A key issue for efficient material processing is the determination of the laser parameters used in the experimental set ups. Despite a systematic investigation that has been performed to highlight the impact of every parameter independently, little attention has been drawn on the role of the substrate material on which the irradiated solid is placed. In this work, the influence of the substrate is emphasised for films of various thicknesses, which demonstrates that both the optical and thermophysical properties of the substrate affect the thermal fingerprint on the irradiated film while the impact is manifested to be higher at smaller film sizes. Two representative materials, silicon and fused silica, have been selected as typical substrates for thin films(gold and nickel) of different optical and thermophysical behaviour and the thermal response and damage thresholds are evaluated for the irradiated solids. The pronounced influence of the substrate is aimed to pave the way for new and more optimised designs of laserbased fabrication set ups and processing schemes.展开更多
The photochemical reaction of potassium ferrocyanide(K_(4)Fe(CN)_(6))exhibits excitation wavelength dependence and non-Kasha rule behavior.In this study,the excited-state dynamics of K_(4)Fe(CN)_(6) were studied by tr...The photochemical reaction of potassium ferrocyanide(K_(4)Fe(CN)_(6))exhibits excitation wavelength dependence and non-Kasha rule behavior.In this study,the excited-state dynamics of K_(4)Fe(CN)_(6) were studied by transient absorption spectroscopy.Excited state electron detachment(ESED)and photoaquation reactions were clarified by comparing the results of 260,320,340,and 350 nm excitations.ESED is the path to generate a hydrated electron(e^(−)_(aq)).ESED energy barrier varies with the excited state,and it occurs even at the first singlet excited state(^(1)T_(1g)).The ^(1)T_(1g) state shows∼0.2 ps lifetime and converts into triplet[Fe(CN)_(6)]4−by intersystem crossing.Subsequently,3Fe(CN)_(5)]^(3-)appears after one CN−ligand is ejected.In sequence,H2O attacksFe(CN)_(5)]^(3-)to generate[Fe(CN)_(5)H_(2)O]^(3−)with a time constant of approximately 20 ps.The ^(1)T_(1g) state and e−aq exhibit strong reducing power.The addition of uridine 5′-monophosphate(UMP)to the K_(4)Fe(CN)_(6) solution decrease the yield of e−aq and reduce the lifetimes of the e−aq and ^(1)T_(1g) state.The obtained reaction rate constant of ^(1)T_(1g) state and UMP is 1.7×10^(14)(mol/L)^(−1)·s^(−1),and the e−aq attachment to UMP is∼8×10^(9)(mol/L)^(−1)·s^(−1).Our results indicate that the reductive damage of K_(4)Fe(CN)_(6) solution to nucleic acids under ultraviolet irradiation cannot be neglected.展开更多
The nonradiative decay of a n-stacked pair of adenine molecules, one of which was excited by an ultrafast laser pulse, is studied by semiclassical dynamics simulations. This simulation investigation is focused on the ...The nonradiative decay of a n-stacked pair of adenine molecules, one of which was excited by an ultrafast laser pulse, is studied by semiclassical dynamics simulations. This simulation investigation is focused on the effect of the formation of bonded excimer in stacked adenines on the mechanism of ultrafast decay. The simulation finds that the formation of the bond- ed excimer significantly lowers the energy gap between the LUMO and HOMO and consequently facilitates the deactivation of the electronically excited molecule. On the other hand, the formation of the chemical bond between two stacked adenines re- stricts the deformation vibration of the pyrimidine of the excited molecule due to the steric effect. This slows down the formation of the coupling between the HOMO and LUMO energy levels and therefore delays the deactivation process of the excited adenine molecule to the electronic ground state.展开更多
基金Projects(862016(Bio Combs4Nanofibres)HELLAS-CH+1 种基金MIS 5002735) funded by the Operational Programme “Competitiveness, Entrepreneurship and Innovation” and co-financed by Greece and the EU (European Regional Development Fund)Project (COST Action TUMIEE) supported by COST-European Cooperation in Science and Technology。
文摘Femtosecond pulsed lasers have been widely used over the past decades due to their capability to fabricate precise patterns at the micro-and nano-lengths scales. A key issue for efficient material processing is the determination of the laser parameters used in the experimental set ups. Despite a systematic investigation that has been performed to highlight the impact of every parameter independently, little attention has been drawn on the role of the substrate material on which the irradiated solid is placed. In this work, the influence of the substrate is emphasised for films of various thicknesses, which demonstrates that both the optical and thermophysical properties of the substrate affect the thermal fingerprint on the irradiated film while the impact is manifested to be higher at smaller film sizes. Two representative materials, silicon and fused silica, have been selected as typical substrates for thin films(gold and nickel) of different optical and thermophysical behaviour and the thermal response and damage thresholds are evaluated for the irradiated solids. The pronounced influence of the substrate is aimed to pave the way for new and more optimised designs of laserbased fabrication set ups and processing schemes.
基金supported by the National Natural Science Foundation of China(No.21873100 and No.21773226)the Open Fund of the State Key Laboratory of Molecular Reaction Dynamics in Dalian Institute of Chemical Physics,Chinese Academy of Sciences。
文摘The photochemical reaction of potassium ferrocyanide(K_(4)Fe(CN)_(6))exhibits excitation wavelength dependence and non-Kasha rule behavior.In this study,the excited-state dynamics of K_(4)Fe(CN)_(6) were studied by transient absorption spectroscopy.Excited state electron detachment(ESED)and photoaquation reactions were clarified by comparing the results of 260,320,340,and 350 nm excitations.ESED is the path to generate a hydrated electron(e^(−)_(aq)).ESED energy barrier varies with the excited state,and it occurs even at the first singlet excited state(^(1)T_(1g)).The ^(1)T_(1g) state shows∼0.2 ps lifetime and converts into triplet[Fe(CN)_(6)]4−by intersystem crossing.Subsequently,3Fe(CN)_(5)]^(3-)appears after one CN−ligand is ejected.In sequence,H2O attacksFe(CN)_(5)]^(3-)to generate[Fe(CN)_(5)H_(2)O]^(3−)with a time constant of approximately 20 ps.The ^(1)T_(1g) state and e−aq exhibit strong reducing power.The addition of uridine 5′-monophosphate(UMP)to the K_(4)Fe(CN)_(6) solution decrease the yield of e−aq and reduce the lifetimes of the e−aq and ^(1)T_(1g) state.The obtained reaction rate constant of ^(1)T_(1g) state and UMP is 1.7×10^(14)(mol/L)^(−1)·s^(−1),and the e−aq attachment to UMP is∼8×10^(9)(mol/L)^(−1)·s^(−1).Our results indicate that the reductive damage of K_(4)Fe(CN)_(6) solution to nucleic acids under ultraviolet irradiation cannot be neglected.
基金supported by the National Natural Science Foundation of China (21073242)the Natural Science Foundation of Chongqing (cstc2011jjA00009)+1 种基金the Project of Science Technology Foundation of Chongqing Education Committee (KJ100507)the Research Fund of Chongqing University of Posts and Telecommunications (A2009-63,A2010-17)
文摘The nonradiative decay of a n-stacked pair of adenine molecules, one of which was excited by an ultrafast laser pulse, is studied by semiclassical dynamics simulations. This simulation investigation is focused on the effect of the formation of bonded excimer in stacked adenines on the mechanism of ultrafast decay. The simulation finds that the formation of the bond- ed excimer significantly lowers the energy gap between the LUMO and HOMO and consequently facilitates the deactivation of the electronically excited molecule. On the other hand, the formation of the chemical bond between two stacked adenines re- stricts the deformation vibration of the pyrimidine of the excited molecule due to the steric effect. This slows down the formation of the coupling between the HOMO and LUMO energy levels and therefore delays the deactivation process of the excited adenine molecule to the electronic ground state.
