Does a Molecule Remember the Way It Was Energized?

1992 ◽  
Vol 57 (6) ◽  
pp. 1157-1172 ◽  
Author(s):  
Milan Šolc ◽  
Zdeněk Herman

Intramolecular vibrational redistribution (IVR) is the key phenomenon in unimolecular decomposition of polyatomic molecules energized in collisions, by photon absorption, or formed by association of radical particles. On an ultrashort time scale, the excitation energy is localized at some place (bond) of the molecule. On a middle time scale, energy irreversibly flows from the excited place to the rest of the molecule. On a long time scale fluctuations of the internal energy are reminiscent of a quasiperiodic process. Almost all the relevant experimental data and model calculations suggest that the information concerning the place of excitation in the molecule is lost during 100 fs - 10 ps after excitation. It seems that due to the rapid IVR the laser selective chemistry has in general no promising perspectives.

1975 ◽  
Vol 48 (2) ◽  
pp. 154-163 ◽  
Author(s):  
L. A. Wood ◽  
G. W. Bullman ◽  
F. L. Roth

Abstract The long-time creep of natural rubber cured with a conventional sulfur-accelerator recipe containing no filler can be conveniently shown near room temperature by a plot of ΔE/E1 with a double-abscissa scale, one marked in units of log t and the other in units of t. When experimental data from the present work and from previous studies reported in the literature are plotted in this manner it is noted that invariably the first scale yields a linear relation at short times and the second a linear relation at long times. The limiting linear relations just mentioned suggest the two-constant Equation (2), already proposed as a general creep equation for many materials. In the case of rubber the range of values of t investigated is from about 10 ms as studied by previous investigators to about 70 days in our work and other studies. Any significant deviations from the equation can be noted by inspection of the double-abscissa plot. We found that the equation furnished an excellent representation of almost all our experimental data up to the longest times. In one instance in our work and in a few other cases there was a prerupture increase of ΔE/E1 above the values given by the equation. This behavior can reduce somewhat the upper limit of validity of the general equation. The constants A and B can be evaluated from experimental observations of ΔE/E1 by solving two simultaneous equations obtained from the values at the longest time, at one minute, and at an intermediate time. In the present work, the constant A was essentially the same (about 2.4%/ (unit log t)) when the atmosphere surrounding the specimen was a vacuum, dry nitrogen, or dry air. The value was raised when the atmosphere was room air at 35% relative humidity and became about 4%/ (unit long t) when the air was saturated with water. The constant B was raised tenfold when the atmosphere was dry air instead of dry nitrogen. It was further increased by a factor of about 2, when the air was saturated. The value of B for the specimen in an atmosphere of stagnant room air was still greater than this by another factor of more than 2. It is possible that this atmosphere contained autocatalytic degradation products or other constituents which were removed when the air was bubbled through water or passed over CaCl2. The approximate boundaries of three different regions of time are determinable from the ratios A/B. In the first region, where t is less than 0.1(A/B), ΔE/E1 is approximately linear with log t. In the second region, where t is between 0.1(A/B) and 4.343 (A/B), ΔE/E1 is not linear with either log t or t. In the third region, where t is greater than 4.343 (A/B), ΔE/E1 is approximately linear with t. A fourth region of anomalous increase preceding rupture is sometimes found, especially when B is large.


Author(s):  
Tian Lu ◽  
Qinxue Chen ◽  
Zeyu Liu

Although cyclo[18]carbon has been theoretically and experimentally investigated since long time ago, only very recently it was prepared and directly observed by means of STM/AFM in condensed phase (Kaiser et al., <i>Science</i>, <b>365</b>, 1299 (2019)). The unique ring structure and dual 18-center π delocalization feature bring a variety of unusual characteristics and properties to the cyclo[18]carbon, which are quite worth to be explored. In this work, we present an extremely comprehensive and detailed investigation on almost all aspects of the cyclo[18]carbon, including (1) Geometric characteristics (2) Bonding nature (3) Electron delocalization and aromaticity (4) Intermolecular interaction (5) Reactivity (6) Electronic excitation and UV/Vis spectrum (7) Molecular vibration and IR/Raman spectrum (8) Molecular dynamics (9) Response to external field (10) Electron ionization, affinity and accompanied process (11) Various molecular properties. We believe that our full characterization of the cyclo[18]carbon will greatly deepen researchers' understanding of this system, and thereby help them to utilize it in practice and design its various valuable derivatives.


Author(s):  
Tian Lu ◽  
Qinxue Chen ◽  
Zeyu Liu

Although cyclo[18]carbon has been theoretically and experimentally investigated since long time ago, only very recently it was prepared and directly observed by means of STM/AFM in condensed phase (Kaiser et al., <i>Science</i>, <b>365</b>, 1299 (2019)). The unique ring structure and dual 18-center π delocalization feature bring a variety of unusual characteristics and properties to the cyclo[18]carbon, which are quite worth to be explored. In this work, we present an extremely comprehensive and detailed investigation on almost all aspects of the cyclo[18]carbon, including (1) Geometric characteristics (2) Bonding nature (3) Electron delocalization and aromaticity (4) Intermolecular interaction (5) Reactivity (6) Electronic excitation and UV/Vis spectrum (7) Molecular vibration and IR/Raman spectrum (8) Molecular dynamics (9) Response to external field (10) Electron ionization, affinity and accompanied process (11) Various molecular properties. We believe that our full characterization of the cyclo[18]carbon will greatly deepen researchers' understanding of this system, and thereby help them to utilize it in practice and design its various valuable derivatives.


2005 ◽  
Vol 70 (3) ◽  
pp. 383-402
Author(s):  
Valery A. Danilov ◽  
Il Moon

This paper is devoted to the development of a new method for estimating mass transfer coefficients and effective area in packed columns in the case of reactive absorption. The method is based on a plug-flow model of reactive absorption of carbon dioxide with sodium hydroxide solution. The parameter estimation problem is solved using an optimization technique. Some mass transfer parameters are found to be correlated. Global sensitivity analysis by Sobol's technique showed that the unit model with the defined objective function is sensitive to the estimated parameter. Case studies of reactive absorption with different packings illustrate application of the proposed method for estimating mass transfer coefficients and effective area from column operation data. The model calculations are compared with experimental data obtained by other authors. The concentration profiles calculated by the unit model with the estimated parameters are shown to match well with experimental profiles from literature. A good agreement between estimated values and experimental data from literature confirms the applicability of this method.


ACS Nano ◽  
2021 ◽  
Author(s):  
I. Meirzada ◽  
N. Sukenik ◽  
G. Haim ◽  
S. Yochelis ◽  
L. T. Baczewski ◽  
...  
Keyword(s):  

2012 ◽  
Vol 25 (6) ◽  
pp. 1963-1995 ◽  
Author(s):  
Zhengyu Liu

Abstract The emerging interest in decadal climate prediction highlights the importance of understanding the mechanisms of decadal to interdecadal climate variability. The purpose of this paper is to provide a review of our understanding of interdecadal climate variability in the Pacific and Atlantic Oceans. In particular, the dynamics of interdecadal variability in both oceans will be discussed in a unified framework and in light of historical development. General mechanisms responsible for interdecadal variability, including the role of ocean dynamics, are reviewed first. A hierarchy of increasingly complex paradigms is used to explain variability. This hierarchy ranges from a simple red noise model to a complex stochastically driven coupled ocean–atmosphere mode. The review suggests that stochastic forcing is the major driving mechanism for almost all interdecadal variability, while ocean–atmosphere feedback plays a relatively minor role. Interdecadal variability can be generated independently in the tropics or extratropics, and in the Pacific or Atlantic. In the Pacific, decadal–interdecadal variability is associated with changes in the wind-driven upper-ocean circulation. In the North Atlantic, some of the multidecadal variability is associated with changes in the Atlantic meridional overturning circulation (AMOC). In both the Pacific and Atlantic, the time scale of interdecadal variability seems to be determined mainly by Rossby wave propagation in the extratropics; in the Atlantic, the time scale could also be determined by the advection of the returning branch of AMOC in the Atlantic. One significant advancement of the last two decades is the recognition of the stochastic forcing as the dominant generation mechanism for almost all interdecadal variability. Finally, outstanding issues regarding the cause of interdecadal climate variability are discussed. The mechanism that determines the time scale of each interdecadal mode remains one of the key issues not understood. It is suggested that much further understanding can be gained in the future by performing specifically designed sensitivity experiments in coupled ocean–atmosphere general circulation models, by further analysis of observations and cross-model comparisons, and by combining mechanistic studies with decadal prediction studies.


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