skip to main content


This content will become publicly available on March 22, 2024

Title: Electronically excited states of closed-shell azabenzene and purine anion structures: Is 2 D enough for dipole-bound excited states?

Deprotonated azabenzene anions require dipole moments in their corresponding neutral radicals of more than 3.5 D in order to exhibit dipole-bound excited states (DBXSs). This is notably larger than the typical 2.0–2.5 D associated with such behavior. Similar computational analysis on deprotonated purine derivatives also conducted herein only requires the more traditional 2.5 D dipole moment, implying that the single six-membered azabenzene rings have additional factors at play in binding diffuse electrons. The present study also shows that the use of coupled cluster singles and doubles with a double-zeta correlation consistent basis set and additional diffuse functions originating from the center-of-charge for all aspects of the computations decreases the error in predicting DBXSs to less than 0.006 eV at worst and likely less than 0.003 eV for most cases. These results can influence the modeling of molecular spectra beyond fundamental chemical curiosity with application to astrochemistry, solar energy harvesting, and combustion chemistry among others.

 
more » « less
Award ID(s):
1757220
NSF-PAR ID:
10440613
Author(s) / Creator(s):
;
Publisher / Repository:
American Institute of Physics
Date Published:
Journal Name:
The Journal of Chemical Physics
Volume:
158
Issue:
12
ISSN:
0021-9606
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Functionalizing deprotonated polycyclic aromatic hydrocarbon (PAH) anion derivatives gives rise to electronically excited states in the resulting anions. While functionalization with −OH and −C 2 H, done presently, does not result in the richness of electronically excited states as it does with −CN done previously, the presence of dipole-bound excited states and even some valence excited states are predicted in this quantum chemical analysis. Most notably, the more electron withdrawing −C 2 H group leads to valence excited states once the number of rings in the molecule reaches three. Dipole-bound excited states arise when the dipole moment of the corresponding neutral radical is large enough (likely around 2.0 D), and this is most pronounced when the hydrogen atom is removed from the functional group itself regardless of whether functionalized by a hydroxyl or enthynyl group. Deprotonatation of the hydroxyl group in the PAH creates a ketone with a delocalized highest occupied molecular orbital (HOMO) unlike deprotonation of a hydrogen on the ring where a localized lone pair on one of the carbon atoms serves as the HOMO. As a result, hydroxyl functionlization and subsequent deprotonation of PAHs creates molecules that begin to exhibit structures akin to nucleic acids. However, the electron withdrawing −C 2 H has more excited states than the electron donating −OH functionalized PAH. This implies that the −C 2 H electron withdrawing group can absorb a larger energy range of photons, which signifies an increasing likelihood of being stabilized in the harsh conditions of the interstellar medium. 
    more » « less
  2. null (Ed.)
    Few anions exhibit electronically excited states, and, if they do, the one or two possible excitations typically transpire beyond the visible spectrum into the near-infrared. These few, red-shifted electronic absorption features make anions tantalizing candidates as carriers of the diffuse interstellar bands (DIBs), a series of mostly unknown, astronomically ubiquitous absorption features documented for over a century. The recent interstellar detection of benzonitrile implies that cyano-functionalized polycyclic aromatic hydrocarbon (PAH) anions may be present in space. The presently reported quantum chemical work explores the electronic properties of deprotonated benzene, naphthalene, and anthracene anions functionalized with a single cyano group. Both the absorption and emission properties of the electronically excited states are explored. The findings show that the larger anions absorption and emission energies possess both valence and dipole bound excitations in the 450–900 nm range with oscillator strengths for both types of >1×10−4. The valence and dipole bound excited state transitions will produce slightly altered substructure from one another making them appear to originate with different molecules. The known interstellar presence of related molecules, the two differing natures of the excited states for each, and the wavelength range of peaks for these cyano-functionalized PAH anions are coincident with DIB properties. Finally, the methods utilized appear to be able to predict the presence of dipole-bound excited states to within a 1.0 meV window relative to the electron binding energy. 
    more » « less
  3. Dicyano-functionalized benzene and naphthalene anion derivatives exhibit a relatively rich population of electronically excited states in stark contrast to many assumptions regarding the photophysics of anions in general. The present work has quantum chemically analyzed the potential electronically excited states of closed-shell anions created by replacing hydrogen atoms with valence-bound lone pairs in benzene and naphthalene difunctionalized with combinations of -CN and -C2H. Dicyanobenzene anion derivatives can exhibit dipole-bound excited states as long as the cyano groups are not in para position to one another. This also extends to cyanoethynylbenzene anions as well as deprotonated dicyano- and cyanoethynylnaphthalene anion derivatives. Diethynyl functionalization is less consistent. While large dipole moments are created in some cases for deprotonation on the -C2H group itself, the presence of electronically excited states beyond those that are dipole-bound is less consistent. Beyond these general trends, 2-dicyanonaphthalene-34 gives strong indication for exhibiting a quadrupole-bound excited state, and the 1-cyanoethynylnaphthalene-29 and -36 anion derivatives are shown to possess as many as two valence-bound excited states and one dipole-bound excited state. These photophysical properties may have an influence on regions where polycyclic aromatic hydrocarbons are known to exist such as in various astrochemical environments or even in combustion flames. 
    more » « less
  4. We report a combined experimental and theoretical investigation of electron–molecule interactions using pyrrole as a model system. Experimental two-dimensional electron energy loss spectra (EELS) encode information about the vibrational states of the molecule as well as the position and structure of electronic resonances. The calculations using complex-valued extensions of equation-of-motion coupled-cluster theory (based on non-Hermitian quantum mechanics) facilitate the assignment of all major EELS features. We confirm the two previously described π resonances at about 2.5 and 3.5 eV (the calculations place these two states at 2.92 and 3.53 eV vertically and 2.63 and 3.27 eV adiabatically). The calculations also predict a low-lying resonance at 0.46 eV, which has a mixed character—of a dipole-bound state and σ* type. This resonance becomes stabilized at one quanta of the NH excitation, giving rise to the sharp feature at 0.9 eV in the corresponding EELS. Calculations of Franck–Condon factors explain the observed variations in the vibrational excitation patterns. The ability of theory to describe EELS provides a concrete illustration of the utility of non-Hermitian quantum chemistry, which extends such important concepts as potential energy surfaces and molecular orbitals to states embedded in the continuum. 
    more » « less
  5. Over the two decades, amorphous oxide semiconductors (AOSs) and their thin film transistor (TFT) channel application have been intensely explored to realize high performance, transparent and flexible displays due to their high field effect mobility (μFE=5-20 cm2/Vs), visible range optical transparency, and low temperature processability (25-300 °C).[1-2] The metastable amorphous phase is to be maintained during operation by the addition of Zn and additional third cation species (e.g., Ga, Hf, or Al) as an amorphous phase stabilizer.[3-5] To limit TFT off-state currents, a thin channel layer (10-20 nm) was employed for InZnO (IZO)-based TFTs, or third cations were added to suppress carrier generations in the TFT channel. To resolve bias stress-induced instabilities in TFT performance, approaches to employ defect passivation layers or enhance channel/dielectric interfacial compatibility were demonstrated.[6-7] Metallization contact is also a dominating factor that determines the performance of TFTs. Particularly, it has been reported that high electrical contact resistance significantly sacrifices drain bias applied to the channel, which leads to undesirable power loss during TFT operation and issues for the measurement of TFT field effect mobilities. [2, 8] However, only a few reports that suggest strategies to enhance contact behaviors are available in the literature. Furthermore, the previous approaches (1) require an additional fabrication complexity due to the use of additional treatments at relatively harsh conditions such as UV, plasma, or high temperatures, and (2) may lead to adverse effects on the channel material attributed to the chemical incompatibility between dissimilar materials, and exposures to harsh environments. Therefore, a simple and easy but effective buffer strategy, which does not require any additional process complexities and not sacrifice chemical compatibility, needs to be established to mitigate the contact issues and therefore achieve high performance and low power consumption AOS TFTs. The present study aims to demonstrate an approach utilizing an interfacial buffer layer, which is compositionally homogeneous to the channel to better align work functions between channel and metallization without a significant fabrication complexity and harsh treatment conditions. Photoelectron spectroscopic measurements reveal that the conducting IZO buffer, of which the work function (Φ) is 4.37 eV, relaxes a relatively large Φ difference between channel IZO (Φ=4.81 eV) and Ti (Φ=4.2-4.3 eV) metallization. The buffer is found to lower the energy barrier for charge carriers at the source to reach the effective channel region near the dielectric. In addition, the higher carrier density of the buffer and favorable chemical compatibility with the channel (compositionally the same) further contribute to a significant reduction in specific contact resistance as much as more than 2.5 orders of magnitude. The improved contact and carrier supply performance from the source to the channel lead to an enhanced field effect mobility of up to 56.49 cm2/Vs and a threshold voltage of 1.18 V, compared to 13.41 cm2/Vs and 7.44 V of IZO TFTs without a buffer. The present work is unique in that an approach to lower the potential barrier between the source and the effective channel region (located near the channel/dielectric interface, behaving similar to a buried-channel MOSFET [9]) by introducing a contact buffer layer that enhances the field effect mobility and facilitates carrier supply from the source to the effective channel region. 
    more » « less