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ARTICLE PREVIEW

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 * Introduction
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 * Cited by (12)


MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING

Volume 153, January 2023, 107119




THEORETICAL STUDY OF 36ADZ BASED ALKALINE EARTHIDES M+(36ADZ)M− (M+ = LI & NA;
M− = BE, MG & CA) WITH REMARKABLE NONLINEAR OPTICAL RESPONSE

Author links open overlay panelAnnum Ahsan, Sehrish Sarfaraz, Faiza Fayyaz,
Maria Asghar, Khurshid Ayub
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https://doi.org/10.1016/j.mssp.2022.107119Get rights and content




HIGHLIGHTS

 * •
   36Adz complexant based alkaline earthides have been successfully designed.
 * •
   The nature of alkaline earthide is confirmed through NBO and FMO analysis.
 * •
   Considerably large NLO responses are observed because of the presence of
   excess electrons on alkaline earth metals.
 * •
   Li+(36Adz)Mg− complex displays the highest hyperpolarizability.


ABSTRACT

The 36Adz complexant has been used to design and investigate another group of
alkaline earthides, M+(36Adz)M−. Here, M+ represents the alkali metals i.e., Li
& Na while M− represents alkaline earth metals i.e., Be, Mg & Ca. Basic pattern
of arrangement of atoms in alkaline earthides includes the insertion of the
alkali metal at the middle of hollow 36Adz cage and the space outside the cage
is occupied by the alkaline earth metal. Natural bond orbitals are scrutinized,
and calculation results show the alkaline earth metals as anions (negative
charges on them). Highest occupied molecular orbitals are also analysed and the
results of this analysis show that highest occupied molecular orbitals are
present on alkaline earth metals. Both these characteristics confirm that the
designed compounds are alkaline earthides. The same characteristic i.e., locale
of excess electron, is further corroborated by the partial density of states
spectra of the compounds. Moreover, extraordinarily higher first
hyperpolarizabilities are shown by these compounds, the highest βo being shown
(equal to 5.1 × 108 au) by Li+(36Adz)Mg−. These inordinately higher values of
hyperpolarizability are ascribed to the distinctive feature of these compounds
i.e., alkaline earth metals incorporate excess electron/bear negative charge.
Furthermore, these complexes show very low transition energies (ΔE) and vertical
ionization energy (VIE) values, ranging from 0.30 to 2.57 eV and
2.24 eV–2.51 eV, respectively. Such lower ΔE and VIE justify their larger values
of hyperpolarizabilities. These results reveal that the alkaline earthides are a
useful entry for high-performance NLO materials.


GRAPHICAL ABSTRACT

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INTRODUCTION

In the recent decades, one of the fast-growing scientific fields is nonlinear
optics. It is centered on the processes related to light matter interactions in
which important role is played by nonlinear response of a system. At the
beginning of the twenty-first century, nonlinear optical (NLO) materials didn't
find large scale commercial applications. However, the situation changed over
the next two decades. Today, NLO materials are one of those materials which are
studied broadly. Such an extensive work is mainly because of the uses of these
materials in various areas such as, optical computing, defense and
telecommunication industries [[1], [2], [3], [4], [5], [6], [7], [8], [9],
[10]]. They are commonly and frequently used in optics and optoelectronics for
storage of information, frequency conversion, processing of images, optical
computing and optical communication [7,[11], [12], [13], [14], [15], [16]].
Both organic [[17], [18], [19], [20]] and inorganic materials [[21], [22], [23]]
are studied for their nonlinear optical properties and many different methods
have been put forward to boost their NLO response. Some of these NLO response
boosting strategies are, electron push pull mechanism through π-conjugation
[24,25], metal ligand frameworks [26], molecules with diradical character [27]
and introduction of excess electron etc. [[28], [29], [30], [31], [32], [33],
[34]]. Introduction of excess electron is the strategy introduced recently and a
lot of work is being done for the introduction of excess electron into compounds
for obtaining better functioning NLO materials. The excess electron in a
compound is the type of electron which is loosely bound to the system and
occupies a diffuse Rydberg orbital [35,36]. Presence of excess electron imparts
fascinating features to molecules and broadens their applications in conductive
[37,38] and optical materials [39,40]. Apart from these applications, excess
electron's loosely bound and dispersive nature brings large nonlinear optical
response in compounds. In 2004, this characteristic of excess electrons i.e.,
role in nonlinear optics was revealed during the study of solvated electron
systems. It was observed that the βo of the molecular cluster (H2O)3 (1.72 × 107
au) consisting of excess electron was higher by six orders of magnitude than its
neutral counterpart (H2O)3 (35 au) lacking such excess electron [41,42]. After
the observation of such a remarkable increase in βo in the presence of excess
electron, it was proposed that such excess electrons which are loosely bound to
the system can be considered as a new outlook to produce new efficient NLO
materials.
Electrides are excess electron compounds which contain the trapped electrons
acting as anions and alkali cations intercalated in complexant molecules [11].
The electride that was prepared by Dye's group for the first time was Cs+ doped
18-crown-6 ether. The synthesis was carried out in the year 1983 by the use of
18-crown-6 ether complexant with cesium (Cs) as an electron source [43]. Other
such electrides studied are alkali metal doped cryptand [2.2.2], (M+(cryptand
[2.2.2]e−), alkali metals doped 15-crown-5 ether, M+(15-crown-5)e− etc. [[44],
[45], [46]]. Subsequently, studies of complexants showed that aza-cryptands are
thermally stable and less reactive because of presence of tertiary amine groups.
By using such stable complexants, Na+(tri-pip-aza 222)e−, first organic
electride was synthesized successfully that was stable at room temperature [47].
Further, theoretical studies continued for stable electrides with effective
nonlinear optical responses. Some of the studied electrides with complexants of
organic nature are; Li+(calix [4]pyrrole)e− (7.33 × 103 au) [48], Li5-
[5]cyclacene (7.9 × 103 au) [49], Li- [9]aneN3 (5.2 × 104 au), Li- [12]aneN4
(6.5 × 104 au), Li- [15]aneN5 (1.2 × 105 au) [50], Li+(tris
[(2-imidazolyl)methyl]amine (TIMA) (1.1 × 106 au) [51]. Some inorganic
complexants containing electrides are Li@B10H14 (2.3 × 104 au) [52],
K+(e@C20F20)- (6.00 × 102 au) and (K3O)+(e@C20F20)- (1.30 × 105 au) [53,54].
Another common system with excess electron is alkalides. Alkalides are the
compounds containing negatively charged alkali metals [55,56]. The intercalation
of alkali metals into various complexants produces electrides but if the alkali
metal atoms are increased in number, the electrides may convert into alkalides
in which excess electron enwraps the alkali metals (other than intercalated
ones), producing alkali anions. Generally, alkalides are compounds comprising of
alkali metal cations (M+) intercalated into complexant with counter alkali metal
anions (M−) [[57], [58], [59]].
After the revelation of role of excess electron in nonlinear optics,
subsequently, electrides and alkalides were frequently studied for their
nonlinear optical properties as both contain excess electrons. Along with
experimental work, theoretical studies continued. Investigations show that the
hyperpolarizabilities of alkalides are larger than those of equivalent
electrides. For example, hyperpolarizability of M+(calix [4]pyrrole)M− (with
cation (M+) as Lithium (Li) and anion (M−) as potassium (K) is about four times
greater as compared to the hyperpolarizability of M+(calix [4]pyrrole)e− (with
cation (M+) as Lithium (Li) [60]. The reason is, alkali metals have smaller
electron affinity value, they cannot hold the enwrapping electron tightly and
such an electron is much more susceptible to external stimuli as compared to the
excess electron of electrides. Some of the studied alkalides are; Li+(NH3)nM−
(M− = Na) where n can be equal to 1–4 (βo up to 7.7 × 104 au) [61], M+(26Adz)M−
and M+(36Adz)M− (M+ and M− = alkali metals, Li, Na, K) (βo up to 3.1 × 105 au)
[62], M+(C6H6F6)M− (here M+ and M− = alkali metals, Li, Na, K) [63] (βo ranging
between 3.49 × 104 au to 1.45 × 106 au).
Moreover, another type of compounds with excess electrons known as alkaline
earthides (alkaline earth metals with negative charge) were introduced in 2018
which show NLO response even larger than alkalides. Their general design
principle includes complexed alkali metals with alkaline earth metals as counter
anions, M+(complexant)M− (M+ = Alkali metals, Li, Na, K intercalated into
complexant while M− = Alkaline earth metals, Be, Mg, Ca present outside the
complexant). In alkaline earthides, the hyperpolarizability of compounds
increases drastically. The reason is that the excess electrons are formed by
contribution of polarized p-electron. Contrary to alkalides where excess
electrons are formed by contribution of polarized s-electron. The alkaline
earthides reported recently for the first time are, M+(C6H6F6)M− (M+ = Alkali
metals Li; M− = Alkaline earth metals Be, Mg and Ca) with βo up to 3.51 × 106 au
[64]. For designing and studying new alkaline earthides showing even enhanced
nonlinear optical properties, continuous efforts are being done. Some other
alkaline earthides studied/reported recently are, M+(NH3)6M− (M+ = Alkali
metals, Li, Na, K; M− = Alkaline earth metals, Be, Mg, Ca) [65] and M+(26Adz)M−
(M+ = Alkali metals, Li, Na; M− = Alkaline earth metals, Be, Mg, Ca) showing βo
up to 5.4 × 105 and 1.0 × 106 au, respectively [66]. Such high NLO responses
drive us to explore them further.
Redko et al. in 2002 successfully synthesized a sodide H+(36Adz)Na−, in which
the source of the excess electron is an encapsulated hydrogen atom [67].
Octupolar 36 adamanzane (36Adz) cage features a stable framework. It consists of
C–N linkages that award it room temperature stability. Zhou et al. investigated
the 3D octupolar electride (Li@36Adz) in order to design nonlinear optical
materials with better properties [68]. Another series of alkalides based on
36Adz complexant is also reported with coinage metals as electron sources,
M+(36Adz)M′ (where M+ = Cu, Ag, and Au; M′ = Li, Na, and K), showing remarkable
NLO response [3]. In this paper, we have reported a comprehensive study of
properties of new series of alkaline earthides. Keeping in view, the features of
36Adz based on the previous reported studies, the designed alkaline earthides
are based on the 36Adz complexant, M+(36Adz)M− (M+ = Alkali metals, Li, Na;
M− = Alkaline earth metals, Be, Mg, Ca).


SECTION SNIPPETS


COMPUTATIONAL METHODOLOGY

Keeping in view the properties of the systems under investigation i.e., charge
transfer and long range (effective over long distances) interactions, a density
functional i.e., ωB97X-D is chosen. ωB97X-D is a DFT-D functional (a hybrid
functional). It possesses the characteristic features like dispersion correction
and long range. These properties enable this functional to give authentic
results for kinetics, thermochemistry, non-covalent interactions [66,69,70] and
transfer of charge especially


GEOMETRICAL CHARACTERISTICS

M+(36Adz)M− (M+ = Alkali metals, Li, Na; M− = Alkaline earth metals, Be, Mg, Ca)
complexes are optimized using density functional, ωB97X-D in combination with
6-31 + G (d,p). Each of the compounds, (Li+(36Adz)Be−, Na+(36Adz)Be−,
Li+(36Adz)Mg−, Na+(36Adz)Mg−, Li+(36Adz)Ca−, Na+(36Adz)Ca−) possesses C1
symmetry in its optimized geometrical form. Moreover, lowest vibrational
frequencies have been computed in order to confirm energy minima of the designed
complexes. The values for Li+(36Adz)M−


CONCLUSIONS

In brief, we have systematically examined the geometrical structures, followed
by the scrutinization of electronic characteristics along with detailed
computation of nonlinear optical characteristics of M+(36Adz)M− complexes by
using ωB97X-D in combination with 6–31G+(d,p) (level of theory). They possess
considerably large nonlinear optical responses which is credited to the excess
electrons occupying alkaline earth metals. The designed compounds reveal higher
nonlinear optical response,


CREDIT AUTHORSHIP CONTRIBUTION STATEMENT

Annum Ahsan: Writing – original draft, Methodology, Investigation,
Conceptualization. Sehrish Sarfaraz: Validation, Software, Methodology. Faiza
Fayyaz: Visualization, Investigation. Maria Asghar: Writing – original draft,
Visualization. Khurshid Ayub: Writing – review & editing, Supervision.


DECLARATION OF COMPETING INTEREST

The authors declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported
in this paper.
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CITED BY (12)


 * THEORETICAL DESIGN OF ALKALINE EARTHIDES M<SUP>+</SUP>(3<SUP>6</SUP> ADZ)
   BE<SUP>−</SUP> (M<SUP>+</SUP> = V, CR, MN, FE, CO, NI, CU, AND ZN) WITH
   EXCELLENT NONLINEAR OPTICAL RESPONSE AND ULTRAVIOLET TRANSPARENCY
   
   2024, Journal of Molecular Graphics and Modelling
   Citation Excerpt :
   
   In these examples alkali metal was coordinated with nitrogen atom and
   fluorine atom in flexible way. Another true alkaline earthides based upon
   36adz complexant was reported by our research group, in which alkali metal
   and alkaline earth metal was used respectively as a source of excess
   electrons shows higher NLO response [56–60]. 56Due to excellent NLO response
   showed by alkaline earthides, we became interested in its designing by using
   transition metals (V–Zn) as a source of excess electrons to check, how
   transition metal metals enhance the electronic and NLO properties of alkaline
   earthides.
   
   Show abstract
   A novel series of alkaline earthides containing eight complexes based upon
   36adz complexant are designed by placing carefully transition metals (V–Zn)
   on inner side and alkaline earth metal outer side of the complexant i.e.,
   M+(36adz) Be− (M+ = V, Cr, Mn, Fe, Co, Ni, Cu and Zn). All the designed
   compounds are electronically and thermodynamically stable as evaluated by
   their interaction energy and vertical ionization potential respectively.
   Moreover, the true nature of alkaline earthides is verified through NBOs and
   FMO study, showing negative charge and excess electrons on alkaline earth
   metal respectively. Furthermore, true alkaline earthides characteristics are
   evaluated graphically by spectra of partial density state (PDOS). The energy
   gap (HOMO -LUMO gap) is very small (ranging 2.95 eV–1.89 eV), when it is
   compared with pure cage 36adz HOMO-LUMO gap i.e., 8.50 eV. All the complexes
   show a very small value of transition energy ranging from 1.68eV to 0.89eV.
   Also, these possess higher hyper polarizability values up to 2.8 x 105au (for
   Co+(36adz) Be−). Furthermore, an increase in hyper polarizability was
   observed by applying external electric field on complexes. The remarkable
   increase of 100fold in hyper polarizability of Zn+(36adz) Be− complex is
   determined after application of external electric field i.e., from 1.7 x 104
   au to 1.7 x 106 au when complex is subjected to external electric field of
   0.001 au strength. So, when external electric field is applied on complexes
   it enhances the charge transfer, polarizability and hyper polarizability of
   complexes and proves to be effective for designing of true alkaline earthides
   with remarkable NLO response.


 * ENHANCED NONLINEAR OPTICAL RESPONSE OF ALKALIDES BASED ON STACKED JANUS
   ALL-CIS-1,2,3,4,5,6-HEXAFLUOROCYCLOHEXANE
   
   2023, Heliyon
   Citation Excerpt :
   
   Many new approaches have been developed such as bond length alternation
   (BLA), bond distances fluctuation, design of octupolar-molecules [3], the
   push-pull mechanism by introducing electron-donating or withdrawing groups
   [4], introducing diradical character and diffuse excess electron strategy etc
   [5–7]. A vast number of organic excess-electron systems with enhanced NLO
   responses have widely been designed by doping metals in organic molecules,
   including cyclic pyrroles [8], polyamines [9], fluorocarbons [6], conducting
   polymers [10–12], graphene quantum dots [13], resulting in alkalide [14–19],
   alkaline earthide [20–23], and electrides [5,24,25], with outstanding NLO
   activity. Alkalides are ionic salt containing alkali metals (such as,
   Li/Na/K) as anion.
   
   Show abstract
   Significant efforts are continuously exerted by the scientific community to
   explore new strategies to design materials with high nonlinear optical
   responses. An effective approach is to design alkalides based on Janus
   molecules. Herein, we present a new approach to remarkably boost the NLO
   response of alkalides by stacking the Janus molecules. Alkalides based on
   stacked Janus molecule, M-n-M' (where n = 2 & 3 while M and M′ are Li/Na/K)
   are studied for structural, energetic, electrical, and nonlinear optical
   properties. The thermodynamic stability of the designed complexes is
   confirmed by the energetic stabilities, which range between -14.07 and
   -28.77 kcal/mol. The alkalide character of alkali metals-doped complexes is
   confirmed by the NBO charge transfer and HOMO(s) densities. The HOMO
   densities are located on the doped alkali metal atoms, indicating their
   alkalide character. The absorptions in UV–Vis and near IR region confirm the
   deep ultraviolet transparency of the designed complexes. The maximum first
   static and dynamic hyperpolarizabilities of 5.13 × 107 and 6.6 × 106 au (at
   1339 nm) confirm their high NLO response, especially for K-2-M′ complexes.
   The NLO response of alkalides based on stacked Janus molecules is 1–2 orders
   of magnitude higher than the alkalide based on Janus monomer. The high values
   of dc-Kerr and electric field-induced response e.g., max ∼107 and 108 au,
   respectively have been obtained. These findings suggest that our designed
   complexes envision a new insight into the rational design of stable high NLO
   performance materials.


 * QUANTUM CHEMICAL APPROACH OF HEXAAMMINE (NH<INF>3</INF>)<INF>6</INF>
   COMPLEXANT WITH ALKALI AND ALKALINE EARTH METALS FOR THEIR POTENTIAL USE AS
   NLO MATERIALS
   
   2023, Journal of Molecular Graphics and Modelling
   Citation Excerpt :
   
   The introduction of excess electrons in an organic or inorganic system is a
   recently developed advanced technique that is now used for enhancing NLO
   characteristics of materials [14–19]. Notable role of electride (excess
   electrons) in increasing first hyperpolarizability is revealed by solvated
   electron systems [20–22]. The hyperpolarizability βo is the NLO property of a
   molecule.
   
   Show abstract
   In this study, nine new electron rich compounds are presented, and their
   electronic, geometrical, and nonlinear optical (NLO) characteristics have
   been investigated by using the Density functional theory. The basic design
   principle of these compounds is placing alkaline earth metal (AEM) inside and
   alkali metal (AM) outside the hexaammine complexant. The properties of nine
   newly designed compounds are contrasted with the reference molecule
   (Hexaammine). The effect of this doping on Hexaamine complexant is explored
   by different analyses such as electron density distribution map (EDDM),
   frontier molecular orbitals (FMOs), density of states (DOS) absorption
   maximum (λmax), hyperpolarizabilities, dipole moment, transition density
   matrix (TDM). Non-covalent interaction (NCI) study assisted with isosurfaces
   has been accomplished to explore the vibrational frequencies and types of
   synergy. The doping of hexaammine complexant with AM and AEM significantly
   improved its characteristics by reducing values of HOMO-LUMO energy gaps from
   10.7eV to 3.15eV compared to 10.7 eV of hexaammine. The polarizability and
   hyperpolarizability (αo and βo) values inquisitively increase from 72 to 919
   au and 4.31 × 10−31 to 2.00 × 10−27esu respectively. The higher values of
   hyperpolarizability in comparison to hexaammine (taken as a reference
   molecule) are credited to the presence of additional electrons. The
   absorption profile of the newly designed molecules clearly illustrates that
   they are highly accompanied by higher λmax showing maximum absorbance in red
   and far-red regions ranging from 654.07 nm to 783.94 nm. These newly designed
   compounds have superior outcomes having effectiveness for using them as
   proficient NLO materials and have a gateway for advanced investigation of
   more stable and highly progressive NLO materials.


 * ANTHRACENE-BRIDGED SENSITIZERS FOR ENVIRONMENTALLY COMPATIBLE DYE-SENSITIZED
   SOLAR CELLS: IN SILICO MODELLING AND PREDICTION
   
   2023, Journal of Molecular Graphics and Modelling
   Citation Excerpt :
   
   Therefore, efforts are being made to design new series of non-fullerene
   acceptor molecules with better efficiency with low toxicity. Various
   theoretical reports are present in the valuable literature in which different
   donor and acceptor molecules have been designed and explored for high
   performance solar cells [17–30]. Chen et al., 2022 synthesized an
   anthracene-bridged organic dye (CXC22) based solar cell in the literature
   [31].
   
   Show abstract
   Advancement in solar cells has gained the attention of researchers due to
   increasing demand and renewable energy sources. Modeling of electron
   absorbers and donors has been performed extensively for the development of
   efficient solar cells. In this regard, efforts are being made for designing
   effective units for the active layer of solar cells. In this study, CXC22 was
   utilized as a reference in which acetylenic anthracene acted as a π bridge
   and infrastructure was D-π-A. We theoretically designed four novel
   dye-sensitized solar cells JU1-JU4 by utilizing reference molecules to
   improve the photovoltaic and optoelectronic properties. All designed
   molecules differ from R by donor moiety modifications. Different approaches
   were done to R and all molecules to explore different analyses like binding
   energies, excitation energies, dipole moment, TDM (transition density
   matrix), PDOS (partial density of states), absorption maxima, and charge
   transfer analysis. For the evaluation of results, we used the DFT technique
   and the findings demonstrated that the JU3 molecule showed a better redshift
   absorption value (761 nm) as compared to all other molecules due to the
   presence of anthracene in the donor moiety which lengthens the conjugation.
   JU3 was proven to be the best candidate among all due to improved excitation
   energy (1.69), low energy band gap (1.93), higher λmax value, and improved
   electron and hole energy values leading toward higher power conversion
   efficiency. All the other theoretically formed molecules exhibited comparable
   outcomes as compared to a reference. As a result, this work revealed the
   potential of organic dyes with anthracene bridges for indoor optoelectronic
   applications. These unique systems are effective contributors to the
   development of high-performance solar cells. Thus, we provided efficient
   systems to the experimentalists for the future development of solar cells.


 * ENHANCEMENT IN NONLINEAR OPTICAL RESPONSE OF OLIGOTHIOPHENES BY INDUCTION OF
   POLARONS
   
   2023, ACS Applied Electronic Materials
   
   


 * RATIONAL DESIGN, STABILITIES AND NONLINEAR OPTICAL PROPERTIES OF
   NON-CONVENTIONAL TRANSITION METALIDES; NEW ENTRY INTO NONLINEAR OPTICAL
   MATERIALS
   
   2023, Materials
   
   

View all citing articles on Scopus

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