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PubMed2003

Time-dependent density functional theory study of the spectroscopic properties related to aggregation in the platinum(II) biphenyl dicarbonyl complex.

Singlet ground-state geometry optimization of the monomer, four dimers, and the trimer of [Pt(bph)(CO)(2)], where bph = biphenyl dianion, was performed at the B3LYP level of density functional theory (DFT) with a mixed basis set (6-311G** on C, O, and H atoms; the Stuttgart/Dresden (SDD) effective core potential (ECP) on the Pt core; [6s5p3d] on the Pt valence shell). The aggregation was based on Pt[bond]Pt binding as well as on pi[bond]pi and electrostatic interactions. The lowest-lying triplet-state geometries of the monomer, one dimer, and the trimer of the complex were also optimized using the above theory. Significant shortening of the Pt[bond]Pt bond was recorded in the triplet state compared to the singlet one. A number of low-energy singlet and triplet allowed excited states were calculated using time-dependent density functional theory (TDDFT) and analyzed with respect to absorption, excitation, and emission spectra collected under various conditions. Simulated spectra of the monomer and dimer based on the singlet excited states were correlated with the absorption spectrum. The emission in concentrated solution was due to the triplet dimer, and the emitting states were (3)MLCT and Pt-centered states.

Journal Article↗
PubMed2001

Influence of hydroxyl substitution on benzyne properties. quantum chemical characterization of the didehydrophenols.

Geometries and singlet-triplet splittings for the 10 geometrical isomers of didehydrophenol are characterized at a variety of levels of electronic structure theory. The influence of the hydroxyl group is primarily to increase/decrease the weight of zwitterionic singlet mesomers that place positive/negative charge adjacent to oxygen in valence bond descriptions of the arynes. For some of the meta isomers, this interaction stabilizes distortion in the direction of a bicyclic geometry. The net effect, relative to the unsubstituted benzynes, is to increase the singlet-triplet splittings in 2,3-, 2,6-, and 3,5-didehydrophenol and to decrease that splitting in 2,4- and 2,5-didehydrophenol (3,4-didehydrophenol is essentially unaffected). As shown for other arynes, the singlet-triplet splittings can also be accurately estimated by correlation with proton hyperfine coupling constants in antecedent monoradicals, these values being accessible from very economical calculations.

Journal Article↗
PubMed2004

Scandium ion-promoted photoinduced electron transfer from electron donors to acridine and pyrene. Essential role of scandium ion in photocatalytic oxygenation of hexamethylbenzene.

Photoinduced electron transfer from a variety of electron donors including alkylbenzenes to the singlet excited state of acridine and pyrene is accelerated significantly by the presence of scandium triflate [Sc(OTf)(3)] in acetonitrile, whereas no photoinduced electron transfer from alkylbenzenes to the singlet excited state of acridine or pyrene takes place in the absence of Sc(OTf)(3). The rate constants of the Sc(OTf)(3)-promoted photoinduced electron-transfer reactions (k(et)) of acridine to afford the complex between acridine radical anion and Sc(OTf)(3) remain constant under the conditions such that all the acridine molecules form the complex with Sc(OTf)(3). In contrast to the case of acridine, the k(et) value of the Sc(OTf)(3)-promoted photoinduced electron transfer of pyrene increases with an increase in concentration of Sc(OTf)(3) to exhibit first-order dependence on [Sc(OTf)(3)] at low concentrations, changing to second-order dependence at high concentrations. The first-order and second-order dependence of k(et) on [Sc(OTf)(3)] is ascribed to the 1:1 and 1:2 complexes formation between pyrene radical anion and Sc(OTf)(3). The positive shifts of the one-electron redox potentials for the couple between the singlet excited state and the ground-state radical anion of acridine and pyrene in the presence of Sc(OTf)(3) as compared to those in the absence of Sc(OTf)(3) have been determined by adapting the free energy relationship for the photoinduced electron-transfer reactions. The Sc(OTf)(3)-promoted photoinduced electron transfer from hexamethylbenzene to the singlet excited state of acridine or pyrene leads to efficient oxygenation of hexamethylbenzene to produce pentamethylbenzyl alcohol which is further oxygenated under prolonged photoirradiation of an O(2)-saturated acetonitrile solution of hexamethylbenzene in the presence of acridine or pyrene which acts as a photocatalyst together with Sc(OTf)(3). The photocatalytic oxygenation mechanism has been proposed based on the studies on the quantum yields, the fluorescence quenching, and direct detection of the reaction intermediates by ESR and laser flash photolysis.

Journal Article↗
PubMed2003

Photochemistry of ortho, ortho' dialkyl phenyl azides.

Phenyl azide, 2,6-diethylphenyl azide, 2,6-diisopropylphenyl azide, and 2,4,6-tri-tert-butylphenyl azide were studied by laser flash photolysis (LFP) methods. LFP (266 nm) of the azides in glassy 3-methylpentane at 77 K produces the transient UV-vis absorption spectra of the corresponding singlet nitrenes. At 77 K, the singlet nitrenes relax to the corresponding triplet nitrenes. The triplet nitrenes are persistent at 77 K and their spectra were recorded. The rate constants of singlet to triplet intersystem crossing were determined at this temperature. LFP of 2,4,6-tri-tert-butyl phenyl azide in pentane at ambient temperature again produces a singlet nitrene, which is too short-lived to detect by nanosecond spectroscopy under these conditions. Unlike the other azides, the first detectable intermediate produced upon LFP of 2,4,6-tri-tert-butyl phenyl azide at ambient temperature is the benzazirine (285 nm) which has a lifetime of 62 ns controlled by ring opening to a didehydroazepine. The results are interpreted with the aid of Density Functional Theoretical and Molecular Orbital Calculations.

Journal Article↗
PubMed2005

Supramolecular photonic therapeutic agents.

A new approach to achieving selectivity for photodynamic therapy based upon the reversible off/on switching of the key therapeutic property (singlet oxygen generation) of a supramolecular photonic therapeutic agent (SPTA) in response to an external stimulus in the surrounding microenvironment is described. A series of SPTA analogues with pH responsive receptors of varying pKa are presented, in which the generation of singlet oxygen is shown to be dependent upon a proton source. For example, systems have been constructed such that the excited state energy of the photosensitizer can be decayed by a rapid photoinduced electron transfer (PET) mechanism, resulting in virtually no singlet oxygen being generated, but when the amine receptor is protonated the PET mechanism does not operate and singlet oxygen is produced. In vitro efficacy demonstrated that the SPTA derivatives can be activated within cells and one analogue is measured to have an EC50 value of 5.8 nM when assayed in the MRC5 cell line.

Benzofurans↗
PubMed2006

Early events in the photochemistry of aryl azides from femtosecond UV/Vis spectroscopy and quantum chemical calculations.

The photochemistry of para- and ortho-biphenylyl azides and 1-naphthyl azide was studied by ultrafast spectroscopy. In every case, the singlet azide second excited states were observed by transient absorption spectroscopy and were found to have lifetimes of hundreds of femtoseconds. The decay of the S(2) states of the azides was accompanied by the growth of transient absorption of the corresponding singlet nitrenes. The intermediate S(1) state of the azides could not be observed due to its low instantaneous concentration resulting from fast fragmentation and nitrene formation. Quantum chemical calculations predict that the S(2) state of the azide is bound and that there is a much lower barrier toward arylnitrene formation from the S(1) state of the azide. Vibrational cooling of para-biphenylnitrene (11 ps) was experimentally observed. The lifetime of singlet ortho-biphenylnitrene was 16 ps in acetonitrile and was not affected by perdeuteration of the aryl ring. The lifetime of singlet 1-naphthylnitrene is 12 ps in acetonitrile at ambient temperature.

Journal Article↗
PubMed2006

Photosensitizing properties of protein hydrolysate-based fertilizers.

The use of protein hydrolysate-based fertilizers (PHF) as adjuvant for pesticides or herbicides has been proposed; however, the behaviors of mixtures of PHFs and pesticides under solar light are not known, and various photochemical reactions may occur. The photosensitizing properties of PHFs were investigated in water solutions (0.8 g of total organic carbon L(-1)) within the wavelength range of 300-450 nm, using furfuryl alcohol (FA) as a probe to test the involvement of singlet oxygen and Irgarol 1051 as an example of organic pollutant. Two commercial PHFs and one standard PHF were studied, all of the products being of animal origin. PHFs photosensitize the transformation of FA (10(-4) M), and the kinetics of FA disappearance follows an apparent first-order rate law. Through the use of sodium azide (1 x 10(-3) M) as singlet oxygen scavenger and deuterium oxide (D2O) for increasing the singlet oxygen lifetime it was shown that singlet oxygen contributes largely to the phototransformation of FA. The replacement of water by D2O increases the apparent first-order rate constant 6 times, whereas the addition of sodium azide reduces it by approximately 90%. These results are confirmed using Irgarol 1051 (10(-5) M). The photosensitizing properties of PHFs might be due to pigments naturally present in tissues from which they are extracted or to compounds generated during the production processes.

Amino Acids↗
PubMed2001

A computational study of tetrahedrene: strained alkene or dicarbene?

A computational study of tetrahedrene at the RCCD/cc-pVDZ level led to a singlet-state structure with a lowest energy vibrational mode of 660 cm(-1). The corresponding triplet state was found to be ca. 37 kcal/mol lower in energy than the singlet state. The heat of formation of the singlet state was estimated to be 270 kcal/mol. An isomeric singlet bicyclic dicarbene bis-bicyclo[1.1.0]cyclobutylidene was found to be approximately 94 kcal/mol lower in energy than tetrahedrene.

Journal Article↗
PubMed2000

Computational study of the electronic structure of substituted phenylcarbene in the gas phase

Gas-phase calculations for ortho-, meta-, and para-substituted phenylcarbenes demonstrate that aromatic ring substituents can have a large effect on the singlet-triplet splitting in these molecules. For example, p-aminophenylcarbene is predicted to have a singlet-triplet splitting (DeltaE(ST)) of 0.7 kcal/mol, which is 4.7 kcal/mol smaller than that of the parent phenylcarbene. However, when the mesomeric effect of pi-donation is removed, as in the meta-substituted molecules, this affect is greatly attenuated. m-Amino substitution lowers the DeltaE(ST) to 5.2 kcal/mol, a change of only 0.2 kcal/mol from the parent phenylcarbene. The sensitivity of phenylcarbene to substitution is judged by the slope of the line correlating the singlet-triplet gaps to linear free energy (LFE) parameters. In this study, the best linear correlation for DeltaE(ST) in the para-substituted phenycarbenes is observed when plotted against sigma(p)(+). The resultant slope (rho) is 5.0. The origin of this effect is preferential interaction of aryl substituents with the singlet rather than the triplet species as demonstrated by electron density analyses.

Journal Article↗
PubMed2002

DFT study of substituted and benzannelated aryl cations: substituent dependency of singlet/triplet ratio.

By using density functional theory (DFT) method at the B3LYP/6-311+G level, it has been shown that the preference for the singlet-state phenyl cation can be dramatically increased relative to the triplet state by introducing onium cationic substituents in the para position. At this level of theory, the singlet ground state for the parent phenyl cation was found to be lower than the triplet by 19.6 kcal/mol. Introduction of electron-donating substituent groups, namely -NMe(2), -NH(2), and -SMe in the para position, strongly favors the triplet state. The -OMe and -SH groups cause a similar but smaller effect, whereas -OH substitution results in an energetically identical system. Protonation of these substituent groups form onium-phenyl dications for which a complete reversal of the relative stabilities in favor of the singlet ground state are indicated with -SH(2)(+), -SMeH(+), and -NH(3)(+) showing the largest singlet/triplet energy difference. The -N(2)(+) group in the para position has a similar effect. Benzannelation also increases the relative stability of triplet aryl cation. Whereas the 1-naphththyl and 2-naphthyl cations are energetically identical, in the 9-anthracenyl cation the triplet minimum lies 13.4 kcal/mol below the singlet minimum. Introduction of activating groups, i.e., OH and NMe(2) at the 4-position of the 1-naphthyl cation, greatly increases the relative stability of the triplet state. Upon heteroatom protonation, the singlet/triplet energy gap is substantially narrowed but the triplet state still remains lower in energy. Structural features in the resulting dications are discussed and compared with the corresponding monocations. The NBO charges at the cationic centers were also compared. We have also calculated the dediazoniation and decarbonylation energetics for mono- and bis-o-trimethylsilyl-substituted benzenediazonium and benzoyl cation to aryl cations in order to probe the effect of beta-silyl stabilization of the positive charge.

Amines↗
PubMed2004

A comparison of acetyl- and methoxycarbonylnitrenes by computational methods and a laser flash photolysis study of benzoylnitrene.

Density functional theory (DFT), CCSD(T), and CBS-QB3 calculations were performed to understand the chemical and reactivity differences between acetylnitrene (CH(3)C(=O)N) and methoxycarbonylnitrene (CH(3)OC(=O)N) and related compounds. CBS-QB3 theory alone correctly predicts that acetylnitrene has a singlet ground state. We agree with previous studies that there is a substantial N-O interaction in singlet acetylnitrene and find a corresponding but weaker interaction in methoxycarbonylnitrene. Methoxycarbonylnitrene has a triplet ground state because the oxygen atom stabilizes the triplet state of the carbonyl nitrene more than the corresponding singlet state. The oxygen atom also stabilizes the transition state of the Curtius rearrangement and accelerates the isomerization of methoxycarbonylnitrene relative to acetylnitrene. Acetyl azide is calculated to decompose by concerted migration of the methyl group along with nitrogen extrusion; the free energy of activation for this concerted process is only 27 kcal/mol, and a free nitrene is not produced upon pyrolysis of acetyl azide. Methoxycarbonyl azide, on the other hand, does have a preference for stepwise Curtius rearrangement via the free nitrene. The bimolecular reactions of acetylnitrene and methoxycarbonylnitrene with propane, ethylene, and methanol were calculated and found to have enthalpic barriers that are near zero and free energy barriers that are controlled by entropy. These predictions were tested by laser flash photolysis studies of benzoyl azide. The absolute bimolecular reaction rate constants of benzoylnitrene were measured with the following substrates: acetonitrile (k = 3.4 x 10(5) M(-1) (s-1)), methanol (6.5 x 10(6) M(-1) s(-1)), water (4.0 x 10(6) M(-1) s(-1)), cyclohexane (1.8 x 10(5) M(-1) s(-1)), and several representative alkenes. The activation energy for the reaction of benzoylnitrene with 1-hexene is -0.06 +/- 0.001 kcal/mol. The activation energy for the decay of benzoylnitrene in pentane is -3.20 +/- 0.02 kcal/mol. The latter results indicate that the rates of reactions of benzoylnitrene are controlled by entropic factors in a manner reminiscent of singlet carbene processes.

Journal Article↗
PubMed2004

2-Silyl group effect on the reactivity of cyclopentane-1,3-diyls. Intramolecular ring-closure versus silyl migration.

Generation of singlet and triplet 2-silylcyclopentane-1,3-diyls and their reactivity have been investigated in the thermal and photochemical denitrogenation of 2,3-diaza-7-silylbicyclo[2.2.1]hept-2-ene. 5-Silylcyclopentene (silyl migration product) is quantitatively obtained, while 5-silylbicyclo[2.1.0]pentane (intramolecular ring-closure product) is not detected in the denitrogenation reactions. Deuterium labeling studies clarify that 5-silylcyclopentene is formed by a suprafacial [1,2] silyl migration in singlet 2-silylcyclopentane-1,3-diyl. UDFT calculations closely reproduce the observed reactivity of the singlet diradical: The enthalpic barriers of the intramolecular ring-closure are calculated to be DeltaH++exo468 = 5.8 kcal/mol and DeltaH++endo468 = 6.7 kcal/mol, which are much higher than the energy barrier for the [1,2] silyl migration, DeltaH++468 = 2.7 kcal/mol. The notable effect of the silyl group on raising the energy barrier of the intramolecular cyclization is rationalized by an electronic configuration of the lowest singlet state of 2-silylcyclopentane-1,3-diyls.

Journal Article↗
PubMed1997

Electronic Structure and Unimolecular Reactions of Cyclopropenone Carbonyl Oxide. A Theoretical Study.

A theoretical investigation on the lowest singlet and triplet potential energy surfaces of cyclopropenone carbonyl oxide 1 is presented. The calculated equilibrium geometry and dipole moment suggest that 1 possesses a strong zwitterionic character. The energy barrier for the isomerization of 1 to the cyclic isomer dioxirane 2 is computed to be 9.4 kcal/mol. The singlet state of 1 dissociates into cyclopropenone and excited singlet oxygen atom ((1)D), while the triplet state of 1 dissociates yielding oxygen atom in its ground state ((3)P). The dissociation process is endothermic for the singlet state but highly exothermic for the triplet.

Journal Article↗
PubMed2005

Efficient emission from charge recombination during the pulse radiolysis of electrochemical luminescent substituted quinolines with donor-acceptor character.

Efficient emission from various donor-acceptor quinolines with an ethynyl linkage (PnQ), which are known as efficient electrogenerated chemiluminescent molecules, was observed with time-resolved fluorescence measurement during the pulse radiolysis in benzene. On the basis of the transient absorption and emission measurements, and steady-state measurements, the formation of PnQ in the singlet excited state can be interpreted by charge recombination between the PnQ radical cation and the PnQ radical anion which are generated initially from the radiolytic reaction in benzene. The strong electronic coupling between the donor and acceptor through conjugation is responsible for the efficient emission during the pulse radiolysis of PnQ in benzene. It is suggested that the positive and negative charges are localized on the donor and acceptor moieties in the radical cation and anion, respectively. This mechanism is reasonably explained by the relationship between the annihilation enthalpy changes and singlet excitation energies of PnQ. The formation of the intramolecular charge transfer state is assumed for PnQ in the singlet excited state with a strong electron donating substituent. The emission from PnQ is suggested to originate from PnQ in the singlet excited state formed from the charge recombination between the PnQ radical cation and the PnQ radical anion during the pulse radiolysis. This is strong evidence for the efficient electrogenerated chemiluminescence of PnQ.

Journal Article↗
PubMed2005

Photoinduced long-lived charge separation in a tetrathiafulvalene-porphyrin-fullerene triad detected by time-resolved electron paramagnetic resonance.

Photoinduced electron transfer has been observed in a molecular triad, consisting of a porphyrin (P) covalently linked to a tetrathiafulvalene (TTF) and a fullerene derivative (C(60)), in the different phases of the liquid crystal E-7 and in a glass of 2-methyltetrahydrofuran (2-MeTHF) by means of time-resolved electron paramagnetic resonance (EPR) spectroscopy. In both solvents, an EPR signal observed immediately after excitation has been assigned to the radical pair TTF(*+)-P-C(60)(*-), based on its magnetic interaction parameters and spin polarization pattern. In the 2-MeTHF glass and the crystalline phase of E-7, the TTF(*+)-P-C(60)(*-) state is formed from the TTF-(1)P-C(60) singlet state via an initial TTF-P(*+)-C(60)(*-) charge-separated state. Long-lived charge separation ( approximately 8 mus) for the singlet-born radical pair is observed in the 2-MeTHF glass at cryogenic temperatures. In the nematic phase of E-7, a high degree of ordering in the liquid crystal is achieved by the molecular triad. In this phase, both singlet- and triplet-initiated electron transfer routes are concurrently active. At room temperature in the presence of the external magnetic field, the triplet-born radical pair (T)(TTF(*+)-P-C(60)(*-)) has a lifetime of approximately 7 mus, while that of the singlet-born radical pair (S)(TTF(*+)-P-C(60)(*-)) is much shorter (<1 mus). The difference in lifetimes is ascribed to spin dynamic effects in the magnetic field.

Journal Article↗
PubMed2005

Experimental and theoretical studies of the C2F4 + O reaction: nonadiabatic reaction mechanism.

In this work, the C(2)F(4)(X(1)A(g)) + O((3)P) reaction was investigated experimentally using molecular beam-threshold ionization mass spectrometry (MB-TIMS). The major primary products were observed to be CF(2)O (+ CF(2)) and CF(3) (+ CFO), with measured approximate yields of % versus %, respectively, neglecting minor products. Furthermore, the lowest-lying triplet and singlet potential energy surfaces for this reaction were constructed theoretically using B3LYP, G2M(UCC, MP2), CBS-QB3, and G3 methods in combination with various basis sets such as 6-31G(d), 6-311+G(3df), and cc-pVDZ. The primary product distribution for the multiwell multichannel reaction was then determined by RRKM statistical rate theory and weak-collision master equation analysis. It was found that the observed production of CF(3) (+ CFO) can only occur on the singlet surface, in parallel with formation of ca. 5 times more CF(2)O(X) + CF(2)(X(1)A(1)). This requires fast intersystem crossing (ISC) from the triplet to the singlet surface at a rate of ca. 4 x 10(12) s(-1). The theoretical calculations combined with the experimental results thus indicate that the yield of triplet CF(2)(ã(3)B(1)) + CF(2)O formed on the triplet surface prior to ISC is < or =35%, whereas singlet CF(2)(X(1)A(1)) + CF(2)O is produced with yield > or =60%, after ISC. In addition, the thermal rate coefficients k(O + C(2)F(4)) in the T = 150-1500 K range were computed using multistate transition state theory and can be expressed as k(T) = 1.67 x 10(-16) x T(1.48) cm(3) molecule(-1) s(-1); they are in agreement with the available experimental results in the T = 298-500 K range.

Journal Article↗
PubMed2005

Quantum chemical study of the mechanism of reaction between NH (X 3sigma-) and H2, H2O, and CO2 under combustion conditions.

Reactions of ground-state NH (3sigma-) radicals with H2, H2O, and CO2 have been investigated quantum chemically, whereby the stationary points of the appropriate reaction potential energy surfaces, that is, reactants, products, intermediates, and transition states, have been identified at the G3//B3LYP level of theory. Reaction between NH and H2 takes place via a simple abstraction transition state, and the rate coefficient for this reaction as derived from the quantum chemical calculations, k(NH + H2) = (1.1 x 10(14)) exp(-20.9 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K, is found to be in good agreement with experiment. For reaction between triplet NH and H2O, no stable intermediates were located on the triplet reaction surface although several stable species were found on the singlet surface. No intersystem crossing seam between triplet NH + H2O and singlet HNO + H2 (the products of lowest energy) was found; hence there is no evidence to support the existence of a low-energy pathway to these products. A rate coefficient of k(NH + H2O) = (6.1 x 10(13)) exp(-32.8 kcal mol(-1)/RT) cm3 mol(-1) s(-1) between 1000 and 2000 K for the reaction NH (3sigma-) + H2O --> NH2 (2B) + OH (2pi) was derived from the quantum chemical results. The reverse rate coefficient, calculated via the equilibrium constant, is in agreement with values used in modeling the thermal de-NO(x) process. For the reaction between triplet NH and CO2, several stable intermediates on both triplet and singlet reaction surfaces were located. Although a pathway from triplet NH + CO2 to singlet HNO + CO involving intersystem crossing in an HN-CO2 adduct was discovered, no pathway of sufficiently low activation energy was discovered to compare with that found in an earlier experiment [Rohrig, M.; Wagner, H. G. Proc. Combust. Inst. 1994, 25, 993.].

Journal Article↗
PubMed2006

Nonadiabatic molecular dynamics simulations of correlated electrons in solution. 2. A prediction for the observation of hydrated dielectrons with pump-probe spectroscopy.

The hydrated dielectron is a highly correlated, two-electron, solvent-supported state consisting of two spin-paired electrons confined to a single cavity in liquid water. Although dielectrons have been predicted to exist theoretically and have been used to explain the lack of ionic strength effect in the bimolecular reaction kinetics of hydrated electrons, they have not yet been observed directly. In this paper, we use the extensive nonadiabatic mixed quantum/classical excited-state molecular dynamics simulations from the previous paper to calculate the transient spectroscopy of hydrated dielectrons. Because our simulations use full configuration interaction (CI) to determine the ground and excited state two-electron wave functions at every instant, our nonequilibrium simulations allow us to compute the absorption, stimulated emission (SE), and bleach spectroscopic signals of both singlet and triplet dielectrons following excitation by ultraviolet light. Excited singlet dielectrons are predicted to display strong SE in the mid infrared and a transient absorption in the near-infrared. The near-infrared transient absorption of the singlet dielectron, which occurs near the peak of the (single) hydrated electron's equilibrium absorption, arises because the two electrons tend to separate in the excited state. In contrast, excitation of the hydrated electron gives a bleach signal in this wavelength region. Thus, our calculations suggest a clear pump-probe spectroscopic signature that may be used in the laboratory to distinguish hydrated singlet dielectrons from hydrated electrons: By choosing an excitation energy that is to the blue of the peak of the hydrated electron's absorption spectrum and probing near the maximum of the single electron's absorption, the single electron's transient bleach signal should shrink or even turn into a net absorption as sample conditions are varied to produce more dielectrons.

Journal Article↗