Ullah 2019

View Article Online
View Journal
NJC
New Journal of Chemistry
Accepted Manuscript
A journal for new directions in chemistry
This article can be cited before page numbers have been issued, to do this please use: F. Ullah, N. Kosar,
K. Ayub, M. Gilani and T. Mahmood, New J. Chem., 2019, DOI: 10.1039/C9NJ00225A.
Volume 40 Number 1 January 2016 Pages 1–846 This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
NJC
New Journal of Chemistry A journal for new directions in chemistry Accepted Manuscripts are published online shortly after
www.rsc.org/njc
acceptance, before technical editing, formatting and proof reading.

Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the

author guidelines.
Please note that technical editing may introduce minor changes

to the text and/or graphics, which may alter content. The journal’s
ISSN 1144-0546 standard Terms & Conditions and the ethical guidelines, outlined
PAPER
in our author and reviewer resource centre, still apply. In no
Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
diarylethene-based metal–organic frameworks
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
rsc.li/njc
Page 1 of 33 New Journal of Chemistry
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3
4
Theoretical study on boron phosphide nanocage doped with superalkalis:
5
6 Novel electrides having significant nonlinear optical response
7
8
New Journal of Chemistry Accepted Manuscript

9 Faizan Ullah,a Naveen Kosar,a Khurshid Ayub,a Mazhar Amjad Gilani*b and Tariq Mahmood*a
10
11
12 *
Corresponding authors
13
14
15 a
Department of Chemistry, COMSATS University Islamabad, Abbottabad Campus, Abbottabad-
16
Published on 11 March 2019. Downloaded on 3/13/2019 6:50:14 AM.
17
18 22060, Pakistan
19
20
21 E-mail: mahmood@cuiatd.edu.pk (T. M.)
22
23 b
24
Department of Chemistry, COMSATS University Islamabad, Lahore Campus, Pakistan
25
26
27
E-mail: mazhargilani@cuilahore.edu.pk (M. A. G.)
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 1
59
60
New Journal of Chemistry Page 2 of 33
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3
4
Abstract
5
6
7 Three series of compounds Li2F@B12P12, Li3O@B12P12 and Li4N@B12P12 are theoretically
8

9 designed and investigated for their nonlinear optical response using density functional theory
10
11 (DFT). Computational results reveal that isomers VIII and X are inorganic electrides whereas
12
13
14 others are excess electron systems. Interaction energies reveal that these systems are quite stable
15
16 and superalkalis are chemisorbed on the nanocage. Doping of B12P12 nanocage with superalkali
17
18 brings a considerable increase in the first hyperpolarizability response of the system. The highest
19
20
21
first hyperpolarizability (βo = 3.48×105 au) along with good ultraviolet transparency is observed
22
23 for isomer III of Li2F@B12P12. Moreover, all three series of compounds are systemically studied
24
25 for the effect of different superalkalis and different doping positions for nonlinear optical response.
26
27
This study will be advantageous for promoting the potential applications of the fullerene-like super
28
29
30 alkalis doped B12P12 nanostructures in the new types of electronic nanodevices and high-
31
32 performance nonlinear optical materials with good ultraviolet transparency.
33
34
35
36
37
38
39
40
41 Keywords: Boron phosphide; Electride; Nonlinear optical (NLO); Superalkali; Density functional
42
43 theory (DFT)
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 2
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3
4
Introduction
5
6
7 Since last two decades, the field of nonlinear optics (NLO) has received ever-increasing scientiﬁc
8

9 interest around the world because of its extensive applications in optical fiber telecommunications,
10
11 optical information storage and optical computing.1–10 Nonlinear optical materials have
12
13
14 widespread uses in laser, optical fibers, optical data handling, optical limiters, optical computing,
15
16 optical waveguides, gyroscopes, scanners, and sensors.11–17 The processing of a large quantity of
17
18 data generated from various sources requires powerful and efficient computers. Optical techniques
19
20
21
can provide several methods of extending the data processing capabilities. Nonlinear optics may
22
23 cater such high computing demands. For this purpose, many new kinds of high-performance NLO
24
25 active organic and inorganic compounds have been designed.18–21 Among different compounds,
26
27
graphene nanoribbons,22 conjugated organic systems,10 metal-ligand structures,23 organic and
28
29
30 inorganic fullerenes are extensively investigated for their nonlinear optical response.24,25 Inorganic
31
32 fullerenes of group III-V, especially nitrides and phosphides nanocages such as (AlN)n, (AlP)n,
33
34 (BN)n, and (BP)n (where n = 12, 24, 36, 48 and so on) have drawn much attention due to their
35
36
37 fascinating properties and applications in electronic devices.26–28 Investigations on different sized
38
39 (XY)n nanocages revealed that nanocages with n = 12 such B12P12, B12N12, Al12N12, Al12P12 are the
40
41 most stable ones.29–31
42
43
44 Doping is an important strategy to tailor the intrinsic characteristics of the fullerenes.24 The above
45
46
mentioned fullerenes are centrosymmetric nano-clusters. Therefore, their first hyperpolarizability
47
48
49 (βo) values are zero. However, by using the strategy of diffuse excess electrons, their NLO response
50
51 can be dramatically enhanced.24,32 Usually, the excess electrons are obtained by doping alkali metal
52
53 atoms on the nanoclusters because of their low ionization potential. However, superalkalis have
54
55
56 even lower ionization potential than alkali metals and therefore can provide excess electrons to the
57
58 3
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 system more easily. Recent studies have confirmed this that superalkalis are better source of excess
4
5
6 electrons for designing clusters having large first hyperpolarizabilities.33–35 Boron Phosphide is an
7
8 interesting material for superalkali doping. Boron Phosphide (BP) 4- and 6-membered rings have

9
10 been synthesized experimentally by Pestana, and Power in 1991.36 Boron Phosphide (BP) is a
11
12
13
refractory semiconducting material with strong covalent binding characteristics for a variety of
14
15 surfaces. Therefore, it is ideal for applications in optoelectronic and microelectronic devices under
16
17 harsh conditions such as harsh environment or high temperature.37 Several reports are found in the
18
19
literature on the adsorption of different molecules on the surface of boron phosphide nanocages.38–
20
21 40
22
23
24
25 In this work, we performed comprehensive DFT computations to investigate how doping of
26
27 superalkalis (Li2F, Li3O, and Li4N) effectively improves the electronic and NLO properties of the
28
29 fullerene-like B12P12 nanocage. Doped fullerene-like X12Y12 (X = Al, B and Y = P, N) nanoclusters
30
31
32 are currently under extensive investigations. However, to our knowledge, no prior detailed
33
34 theoretical investigations regarding the adsorption of superalkalis (Li2F, Li3O, and Li4N) on the
35
36 surface of boron phosphide nanocages is reported in the literature.
37
38
39 First superlkali cation (Li3O+) was observed in the crystal of Li3O+NO2 in 1938 41
and in 1979,
40
41
42
isolated superalkali Li3O was observed for the first time during the mass spectrometric analysis of
43
44 solid lithium oxide.42 In 1970, Kollman et al. first predicted the existence of lithium-rich fluoride
45
46 species when they have found a stable structure of Li3F in their theoretical study.43 Peter K. Pearson
47
48 et al. in 1973 calculated thermodynamical stability of Li2F.44 Whereas it was more accurately
49
50
51 investigated by Gutowski and Simons in 1994 using ab initio molecular orbital theory calculations.
52
53 Gutsev and Boldyrev calculated the electronic structure of Li4N in 1982.45 Since from their
54
55
56
57
58 4
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 discovery, superalkalis have been studied extensively for their electride and non-linear optical
4
5
6 properties.
7
8

9 We have focused specifically on these issues; (i) Can the superalkali effectively bind with the
10
11 B12P12 nanocluster with considerable binding energies? (ii) Can the excess electron be produced
12
13 as the superalkali interacts with the B12P12 nanocluster? (iii) If the excess electrons are introduced,
14
15
16
can it cause large first hyperpolarizability response for these superalkali doped B12P12 nanocluster?
17
18 (iv) How will superalkali affect the electronic property of B12P12 nanocluster with wide HOMO-
19
20 LUMO energy gap (EH-L). By resolving these issues, this study will provide some new valuable
21
22
insights into the design of superalkali doped B12P12 nanodevices with excellent electronic
23
24
25 properties as well as significantly higher NLO response.
26
27
28 Computational methods
29
30 Geometry optimization of a series of Li2F@B12P12, Li3O@B12P12 and Li4N@B12P12 nanoclusters
31
32
33 is performed at B3LYP/6-31+G (d) level of theory. Becke’s hybrid 3-parameter exchange
34
35 functional (B3)46 and Lee-Yang-Parr’s correlation functional (LYP)47 in conjunction with 6-31+G
36
37 (d) basis set is a reliable method for the geometry optimization of similar systems, as revealed
38
39
40 from recent studies.24,33,48–50 A number of possible orientation of superalkali on Boron Phosphide
41
42 nanocages are considered. Frequency calculations, performed at B3LYP/6-31+G(d) level, revealed
43
44 that the optimized structures correspond to real local minima (absence of imaginary frequencies).
45
46
The stabilities of these superalkali doped boron phosphides are judged from binding energies
47
48
49 which are calculated at the B3LYP/6-31+G(d) level.
50
51 The interaction energy is defined as:
52
53 Eint = Esuperalkali@B12P12 - (EB12P12 + Esuperalkali) Equation 1
54
55
56
57
58 5
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 where E(B12P12), E(superalkali), and E(superalkali@B12P12) are the total energies of the undoped
4
5
6 B12P12 nanocage, corresponding superalkali unit (Li2F, Li3O, and Li4N), and doped system,
7
8 respectively.

9
10 Moreover, other properties such as natural bond orbital (NBO), dipole moment (µo), highest
11
12
13
occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy gap,
14
15 vertical ionization energy (VIE) and ultraviolet-visible-infrared (UV-VIS-NIR) absorption spectra
16
17 are also calculated.

18
19
Polarizability (αo) and first hyperpolarizability (βo) of all the considered systems in this study are
20
21
22 calculated at LC-BLYP/6-31+G(d) level of theory. LC-BLYP is a full range-separated functional
23
24 having correct 1.00 fraction of nonlocal exchange at asymptotic distance. Earlier studies have
25
26 reported that a full range-separated functional at asymptotic distance (such as LC -BLYP or
27
28
29 ωB97XD) can give better estimates of nonlinear optical properties compared to functionals which
30
31 do not incorporate a full range-separation such as CAM-B3LYP (0.65 fraction of nonlocal
32
33 exchange) or B3LYP.51–54
34
35
36
The mean polarizability (αo) and hyperpolarizability (βo) are defined as follows:
37
38 αo = 1/3(αxx+ αyy+ αzz) Equation 2
39
40 βo = [βx2 + βy2 + βz2]1/2 Equation 3
41
42
where βx = βxxx + βxxy + βxxz, βy = βyyy+ βyzz+ βyxx and βz = βzzz+ βzxx+ βzyy
43
44
45 The time-dependent density functional theory (TD-DFT) calculations are performed at the TD-
46
47 B3LYP/6-311+G (d) level to get the crucial excitation energies (∆E) and oscillator strength (f).33
48
49 All the calculations are carried out by using the Gaussian 09 program package.55 Molecular
50
51
52 structures and orbitals are generated with the GaussView program.56 The density of states (DOS)
53
54 and partial density of states (PDOS) of all the structures are plotted by using multiwfn software 57.
55
56
57
58 6
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3
4
Results and discussion
5
6 Optimized geometries of superalkali doped boron phosphide nanocages
7
8

Boron phosphide (B12P12) nanocage is optimized with no symmetry constrain conditions at
9
10
11 UB3LYP/6-31+G (d) level of theory using GAUSSIAN 09 package. The optimized structure of
12
13 B12P12 nanocage is given in the Figure 1. It comprises six tetragons and eight hexagons. Two
14
15 distinct B-P bonds, b66 and b64, are observed in the optimized structure of the nanocage. The former
16
17
18
connects two six-membered rings, whereas the latter is fused between a tetragon and a hexagon
19
20 ring. The b66 and b64 bonds lengths are 1.91 Å and 1.93 Å, respectively. Two symmetry operations
21
22 E (the identity operation) and σ (a mirror plane) are observed for the optimized geometry of B12P12
23
24
nanocage i.e. and it belongs to the Cs point group.
25
26
27 All possible geometries of superalkalis (Li2F, Li3O, and Li4N) doped boron phosphide (B12P12)
28
29 nanocages are considered for optimization, but eleven (10) of those are converged to stable
30
31 structures. Three stable structures (I-III) are obtained from doping of Li2F on B12P12 nanocluster.
32
33
34 When Li2F is doped on the nanocluster, the interactions become dominated between Li of the
35
36 superalkali and P atoms of nanocluster. In parallel, interaction between F atom of superalkali and
37
38 B atom of the nanocage occurs. However, the structural integrity of the cage and superalkali is
39
40
41
rarely changed during doping. The isomer I is the most stable isomer among all optimized
42
43 structures of Li2F@B12P12 isomers. The isomer I has C1 symmetry. In I, Li2F is present in the
44
45 center of the 4-membered ring. Li atoms of superalkali are fixed on the top of the P atoms of the
46
47
four-membered ring. While F atom (superalkali) and B atom (nanocage) don’t interect in this
48
49
50 isomer. The calculated Li-F bond length is 1.69 Å in isomer I, as compared to 1.67 Å in isolated
51
52 superalkali. The bond angle of superalkali (∠LiFLi) in isomer I is also reduced to 121.91°
53
54
55
56
57
58 7
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 compared to 177.75° in isolated superalkali. However, the average bond length of Li-P bond is
4
5
6 2.46 Å.
7
8 Another isomer II is optimized in which Li2F is present on the top of the six-membered ring. Each

9
10 Li atom of superalkali is fixed on the top of the P atom of the cage and F atom of the superalkali
11
12
13
is adjusted on the top of the B atom of the ring. In isomer II, average bond length of Li-P is 2.48
14
15 Å and bond angle of superalkali (∠LiFLi) is reduced to 120°. The calculated Li-F bond length is
16
17 1.69 Å, comparable to the ones observed in isomer I. Another stable isomer III is obtained where
18
19
20
Li2F is present over the center of the six-membered ring. Two Li atoms are positioned on top of B
21
22 and P atom of the ring. Average bond length of Li-P is 2.546 Å and bond angle of superalkali
23
24 (∠LiFLi) is 126.24° (see Table 1).
25
26
As a result of doping Li3O with B12P12 nanocage, four stable isomers of Li3O@B12P12 (IV-VII) are
27
28
29 observed. Similar to Li2F@B12P12 complexes, the structural integrity of the B12P12 cage and Li3O
30
31 superalkali remains intact. Interactions between atoms of the superalkali (lithium and oxygen) and
32
33 atoms of nanocage (phosphorus and boron, respectively) are observed. Isomer IV is the most stable
34
35
36 isomer among all Li3O doped (Li3O@B12P12) isomers. In IV, O atom of Li3O is placed on the top
37
38 of B atom, while each Li atom of superalkali is confined at the top of P. The bond angle of
39
40 superalkali (∠LiOLi) is subjected to a less significant change (from 120° to 119.8°) in the doped
41
42
43 complexes compared to Li2F doped system. Because of interactions with the cage, the bond length
44
45 between Li-O bond is weakened and Li-O bond is stretched to 1.80 Å from 1.68 Å (of individual
46
47 Li3O unit). The bond lengths of Li-P and O-Al bonds are 2.36 Å and 1.50 Å, respectively. In V, O
48
49
50
atom of the superalkali occupies the center of the six-membered ring and each Li atom is fixed on
51
52 top of P. The average bond length of Li-P bond is 2.57 Å. B and O atoms don’t interact in this
53
54 isomer. Compared to isomer IV, the interaction between superalkali and cage is weaker, therefore
55
56
57
58 8
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 shorter O-Li bond length of 1.69 Å is observed in isomer V. Bond angle (∠LiOLi) is further
4
5
6 reduced to 113.84°. The vertical placement of Li3O on the B12P12 nanocage generates another
7
8 isomer VI, in which the two Li atoms of superalkali are directed towards the P of the 4-membered

9
10 ring. The O atom occupies the center position of 4-membered ring where the O-B bond is cutoffed.
11
12
13 Another stable isomer VII is obtained where Li3O is vertically placed on fused bonds of b66 and
14
15 b64. In this isomer, two Li atoms are directed towards P atoms while O atom of superalkali is fixed
16
17 on top of B atom of the nanocage. In both isomers VI and VII, the ∠LiOLi is 120.0° and the
18
19
20
average bond length of Li-O is 1.69 Å, similar to individual superalkali. Whereas, the bond length
21
22 of Li-P bond (2.49 Å) of isomer VI is slightly shorter from the bond length of Li-P bond (2.51 Å)
23
24 of isomer VII.
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 9
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3
4
5
6
7
8

9
10
11
12
13
Pure B12P12 I II III
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
IV V VI VII
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43 VIII IX X
44
45 Figure 1: Optimized geometries of Li2F@B12P12, Li3O@B12P12 and Li4N@B12P12 isomers
46
47
48
49
50 Capping of B12P12 with Li4N in different orientations and optimization at B3LYP/6-31+G(d) level
51
52 of theory resulted in the three stable isomers i.e. VIII, IX and X. In all these three isomers,
53
54
55
geometric integrity of the nanocage remained intact like the individual nanocage. Isomer VIII is
56
57
58 10
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 the most stable as a result of the strong interaction between superalkali and nanocage. In this
4
5
6 isomer VIII, Li4N subunit binds with the B12P12 cage via three Li-P bonds and one B-N bond. It
7
8 is discerned that three Li atoms of Li4N are confined by the three P atoms of B12P12 nanocage in

9
10 this isomer. Whereas, one Li atom is pointed in upward in opposite direction to the B 12P12 cage.
11
12
13 The average angle ∠LiNLi is increased from 90.0° to 105.7°. The bond length of N-Li bond in
14
15 Li4N@B12P12 isomer is elongated to 1.87 Å, compared to the isolated Li4N (1.82 Å), which may
16
17 be attributed to the fact that the formation of N-B and Li-P bonds weakens the bond strength of N-
18
19
20
Li bond. The bond length of N-B bond and average bond length of Li-P bonds are 1.44 Å and 2.38
21
22 Å, respectively. Isomer IX is generated, by capping the Li4N subunit on a 6-membered ring of the
23
24 B12P12 nanocage. The geometry of IX is such that three Li atoms are directed toward three P atoms
25
26 of the six-membered ring, whereas B and N atoms don’t interact in this isomer. The fourth Li atom
27
28
29 of the superalkali is directed vertically away from the cage. The average bond length of the Li-P
30
31 bonds is 2.58 Å and average bond length of N-Li is 1.78 Å. Whereas, average angle ∠LiNLi is
32
33 further increased to 109.16° as compared to (105.69°) isomer VIII. Isomer X is generated by
34
35
36 placing N atom above B atom and three Li are directed towards three P atoms along b64, b64, and
37
38 b66 bonds. While the fourth Li is directed vertically away from the cage. The ∠LiNLi is 107.38°,
39
40 the average bond length of the three Li-P bonds is 2.44 Å and Li-N bond length is 1.91 Å. All
41
42
43 these isomers of the three series have C1 symmetry.
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 11
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 Table 1: Relative energies Erel (in kcal mol-1), symmetry (Sym.), first frequency ν1 (in cm-1),
4
5 average bond length between Li and P (XLi-P in Å), average bond length between F/O/N and Li
6 (Xx-Li in Å), bond angle between Li, F/O/N and Li (∠LiXLi in degree) and interaction energy (Eint)
7 in kcal mol-1 of all optimized isomers.
8

9
10
11 Li2F@B12P12
12
13
14 Isomers Erel. Sym. ν1 XLi−P XX−Li ∠LiXLi Eint
15
16 I 0 C1 13.96 2.46 1.69 121.9 -42.33
17
18
II 0.52 C1 31.18 2.48 1.68 120.1 -41.81
19
20
21 III 2.74 C1 51.37 2.55 1.68 126.2 -39.59
22
23 Li3O@B12P12
24
25
Isomers Erel Sym. ν1 XLi−P XO−Li ∠LiOLi Eint
26
27
28 IV 0 C1 80.17 2.36 1.80 119.8 -67.93
29
30 V 25.36 C1 59.97 2.57 1.69 113.8 -42.58
31
32
33
VI 27.90 C1 12.38 2.49 1.69 120.0 -40.03
34
35 VII 27.99 C1 21.41 2.51 1.69 120.0 -39.94
36
37 Li4N@B12P12
38
39
40
Isomers Erel Sym. ν1 XLi−P XN−Li ∠LiNLi Eint
41
42 VIII 0 C1 48.26 2.38 1.87 105.7 -100.12
43
44 IX 43.2 C1 52.36 2.58 1.78 109.2 -56.92
45
46
47 X 57.08 C1 60.94 2.44 1.91 107.4 -43.04
48
49
50
51
52 Stability and electride characteristics
53
54 For analyzing the stability of all optimized isomers, the energy gap between the highest occupied
55
56 molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) and their
57
58 12
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 interaction energies (Eint) are calculated. Systems with higher HOMO-LUMO energy gap (EH-L
4
5
6 gap) are chemically stable. All these superalkali doped boron phosphide complexes have stable
7
8 EH-L gap (1.09 eV to 1.59 eV) except isomers IV and VIII, which possess EH-L gap of 0.97 eV and

9
10 0.69 eV, respectively (Table 2). The EH-L gaps of doped system are comparable to the kinetically
11
12
13
stable C60 fullerene (1.57 eV),58 indicating that these superalkali doped boron phosphide
14
15 complexes are chemically stable. The frontier molecular orbitals (FMOs) analysis of pure B12P12
16
17 shows that boron phosphide nanocage has a large EH-L gap of 3.67 eV. B12P12 is a large band gap
18
19
semiconductor which limits its application in optoelectronic as efficient NLO material. To enhance
20
21
22 the conducting properties of boron phosphide nanocage, boron phosphide is capped with
23
24 superalkalis (Li2F, Li3O, and Li4N), and, as a result, the EH-L gap is significantly reduced.
25
26 Molecular orbitals of all the superalkali doped boron phosphide nanocages are analyzed. The
27
28
29 reason for the decrease in the EH-L gap is the increase in the energies of HOMOs and decrease in
30
31 the energies of LUMO after doping. The energies of HOMOs are increased due to the presence of
32
33 excess electrons. These electrons are diffused from the superalkalis towards nanocage. The diffuse
34
35
36
electrons occupy the new energy levels which are now known as HOMO and the old ones become
37
38 HOMO-1, as reported earlier in the literature.28 Analyzing the data, the EH-L gap of superalkali
39
40 doped B12P12 is narrowed between 41% to 63% as compared to that of pure nanocage. The lowest
41
42
EH-L gap (0.69 eV) is observed for isomer VIII of Li4N series. In isomers VIII and X, the electronic
43
44
45 density (in HOMOs) reside outside any atom (in an empty space) which justifies the electride
46
47 properties of these isomers. Rest of the isomers have electronic density concentrated on the atoms
48
49 of the cage. The high concentration of the electronic density on the cage represents the shifting of
50
51
52 electronic density from the superalkali toward the cage. The excess electrons are pushed out from
53
54 the outer s valence orbital of alkali atoms (of the superalkali units) under the action of lone pairs
55
56
57
58 13
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 of the P atoms. The excess electrons can eﬀectively increase the energy of newly formed HOMO,
4
5
6 which results in the narrowing of the HOMO-LUMO energy for these doped systems. Hence, these
7
8 superalkalis can be effectively used to decrease wide HOMO-LUMO energy gap of boron

9
10 phosphide nanocage and increase its potential application in nanoscale electronic devices in future.
11
12
13 The vertical ionization energies (VIE) also support the high stability of these newly designed
14
15
16
electrides (VIII and X) and excess electron systems (see Table 2). All the isomers have VIE values
17
18 from 3. 31 kcal mol-1 to 4.16 kcal mol-1.
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 14
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3
4 Li2F@B12P12
5
6 HOMO LUMO HOMO LUMO
7
8

9
10
11
12
13
14
15 (I) (II)
16
17
18
19
20
21
22
23 (III)
24
25
26
27 Li3O@B12P12
28
30
31
32
33
34
35
36
37
38
39 (IV) (V)
40
41
42
43
44
45
46
47
48 (VI) (VII)
49
50
51
52
53
54
55
56
57
58 15
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3
4 Li4N@B12P12
5
6
7

9
10
11
12
13
14
15
16
17 (IX)
18 (VIII)
19
20
21
22
23
24
25
26
27
(X)
28
29
30
31 Figure 2: HOMOs and LUMOs of Li2F@B12P12, Li3O@B12P12 and Li4N@B12P12 isomers
32
33 (Isovalue = 0.05)
34
35
36
37
38 Furthermore, all these superalkali@B12P12 isomers (I-X) exhibit fairly large interaction energies
39
40
41
(-39.5 kcal mol-1 to -100.12 kcal mol-1). The large interaction energies suggest chemisorption of
42
43 superalkali over the cage. The Eint is the negative of the intermolecular interaction energy between
44
45 the superalkali and pure nanocage. Thus, the larger the Eint value, the stronger is the interaction
46
47
between two subunits and greater is the stability of resultant complex. The Eint values range from
48
49
50 -39.5 kcal mol-1 to -100.12 kcal mol-1of superalkali@ B12P12 and these are larger than those of
51
52 alkali metal doped B12P12 compounds (-7.41 kcal mol-1 to -20.31 kcal mol-1) 40 mainly due to the
53
54 number of interaction present between superalkali and nanocage. These results indicate the
55
56
57
58 16
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 stronger interaction of superalkalis (Li2F, Li3O and Li4N) to B12P12 nanocage than alkali metal
4
5
6 atoms. Thus, compared to alkali metal doped B12P12, capping B12P12 nanocage with superalkalis
7
8 not only produces more structural isomers, but also generate more stable compounds.

9
10
11 To study the extent of charge transfer, the NBO charges on superalkali units are analyzed and
12
13 given in Table 2. Charge analysis data from NBO confirmed the charge transfer from the
14
15
16
superalkali unit to the nanocage in all the doped isomers. The charge transfer is evident from the
17
18 positive charges present on the alkali metal atoms in the superalkali unit and the net positive charge
19
20 on the superalkali unit. From table 2, the NBO charges on superalkali units in Li2F doped
21
22
complexes are observed between 0.80 |e| to 0.828 |e|, while in case of Li3O and Li4N doped series,
23
24
25 these range between 0.797 |e| to 1.105 |e| and 0.529 |e| to 0.753 |e|, respectively. Among all newly
26
27 designed isomers, the highest charge is observed for isomer IV of Li3O@B12P12. On the other side,
28
29 the lowest charge is observed for isomer VIII of Li3O@B12P12
30
31
32 Charge is transferred from the superalkali units to the nanocage. The excess electrons are pushed
33
34
35 out from the outer s valence orbital of alkali atoms (of the superalkali units) under the action of
36
37 lone pairs of the P atoms. Whereas, electronegative atoms (F, O and N) of the superalkalis interact
38
39 with the B atom of the cage and withdraw the electronic density towards the superalkalis. Overall,
40
41
42
excess electrons are pushed from superalkalis towards the nanocages. A more pronounced charge
43
44 transfer is observed as compared to the previously reported charges (0.531–0.634 |e|) on alkali
45
46 metal atoms in M@Al12N12 (M = Li, Na, K) complexes.24
47
48
49
50
51
52
53
54
55
56
57
58 17
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 Table 2: NBO charges on superalkalis (Q in |e|), Energies of HOMOs (in eV), energies of LUMOs
4
5
(in eV), HOMO-LUMO gaps (in eV), VIE (in eV) and wavelength (λmax in nm).
6 Isomers Q HOMO LUMO EH-L VIE λmax
7
8 Pure B12P12 - -6.92 -3.26 6.92 -

3.67
9
10
11
Li2F@B12P12
12 I 0.82 -4.03 -2.49 1.53 4.03 563.24
13
14 II 0.83 -3.99 -2.5 1.50 3.99 586.63
15
16 III 0.81 -3.96 -2.49 1.46 3.96 756.06
17
18 Li3O@B12P12
19
20 IV 1.11 -3.31 -2.34 0.97 3.31 1730.93
21
22 V 0.80 -3.85 -2.33 1.51 3.85 876.24
23
24
VI 0.81 -3.66 -2.17 1.49 3.66 596.39
25 VII 0.82 -3.63 -2.15 1.48 3.63 747.34
26
27 Li4N@B12P12
28
29 VIII 0.55 -3.61 -2.92 0.69 3.61 429.51
30
31 IX 0.75 -3.68 -2.17 1.51 3.68 887.44
32
33 X 0.53 -3.69 -2.59 1.09 3.69 648.2
34
35
36
37
38 PDOS and TDOS analysis
39
40
41 For further confirmation of the electronic behavior of these superalkali doped isomers, partial
42
43 density of states (PDOS) and total density of states (TDOS) analyses are also performed. PDOS
44
45
46
and TDOS of pure nanocage and the most stable superalkali doped nanocages are plotted in Figure
47
48 3 (rest are provided in supplementary information). All these DOS spectra indicate the contribution
49
50 of superalkalis fragment and nanocage fragment towards the variation of energy levels of HOMOs
51
52
and LUMOs. The increase and decrease of HOMOs/LUMOs energies caused reduction in energy
53
54
55 of EH-L gap. Doping superalkalis on B12P12 nanocage created new energy levels, as a result of the
56
57
58 18
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 transfer of excess electrons from superalkalis to nanocage. The newly generated HOMOs have
4
5
6 higher energy compared to the energies of HOMOs of pure nanocage.
7
8

9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
Figure 3: TDOS and PDOS spectra of most stable complexes (I, IV and VIII) of
55
56 superlaklis@B12P12.
57
58 19
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 Absorption analysis
4
5
6 High performance NLO materials are mainly used in second harmonic generation (SHG) for
7
8

9 doubling frequency. Therefore, good NLO materials should have transparency under the utilized
10
11 laser light. To investigate transparency of the newly designed superalkali doped boron phosphide
12
13 complexes, the ultraviolet visible infrared (UV-VIS-NIR) absorption analysis is performed and
14
15
16
spectra of stable isomers from each superalkali set are shown in Figure 4. The main absorption
17
18 regions of all isomers lie in the range above UV region. In Li2F@B12P12 series, the highest λmax of
19
20 756.06 nm is observed for the isomer III which has the lowest EH-L (1.46 eV). The highest λmax
21
22
(1730.93 nm) is observed for the isomer IV of Li3O@B12P12 series which has the lowest EH-L (0.97
23
24
25 eV), whereas the lowest λmax (596.39 nm) is observed for the isomer VI of Li3O@B12P12 having
26
27 the highest EH-L (1.48 eV). Isomer VIII of Li4N@B12P12 series, have the lowest EH-L of 0.69 eV
28
29 and λmax value of 429.51 nm. The isomer IX has higher EH-L of 1.51 eV with higher λmax of 887.44
30
31
32 nm. All isomers have weak absorption in the visible and ultraviolet region which indicates
33
34 sufficient transparency for the routinely used laser applications. Also, these excess electron
35
36 systems and electrides (VIII and X) are fully transparent in deep ultraviolet region (≤200 nm), so
37
38
39
these systems may be considered as new candidates for deep ultraviolet high performance NLO
40
41 materials.
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 20
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3
4
5 Li2F@B12P12
6
7
8

9
10
11
12
13
Transparent region
14
15
16
17
18
19
20
21 Li3O@B12P12
22
23
24
25
26
27
28
29 Transparent
30 region
31
32
33
34
35
36
37
Li4N@B12P12
38
39
40
41
42
43
44
45 Transparent
46 region
47
48
49
50
51
52
53
54 Figure 4: The UV-VIS-NIR Absorption spectra of superalkali@B12P12 isomers (I-X).
55
56
57
58 21
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 Nonlinear optical (NLO) properties
4
5
6 It is previously reported in the literature that NLO response of a system can be enhanced effectively
7
8

9 by introducing the excess electrons to the system. The excess electrons occupy the high energy
10
11 HOMOs which cause the reduction of EH-L gap of corresponding system and results in the increase
12
13 of first hyperpolarizability (βo) values. First hyperpolarizability (βo) is a decisive factor for NLO
14
15
16
response of any system. Previously, doping of alkali metals on the different fullerenes is reported
17
18 as an efficient strategy for enhancing NLO response. In this work, the stable inorganic superalkali
19
20 doped B12P12 nanocages are designed and are expected to have large NLO response. Hence, the
21
22
dipole moments (µo), polarizabilities (αo), and first hyperpolarizabilities (βo) of these
23
24
25 superalkali@B12P12 nanostructures are computed and given in Table 3. As isolated B12P12
26
27 nanocage is centrosymmetric, therefore first hyperpolarizability (βo) and dipole moment of pure
28
29 nanocage are zero. The doping of superalkalis brings significant enhancement of the dipole
30
31
32 moment (µo) and first hyperpolarizability (βo) for the B12P12 nanocage. This is due to the distortion
33
34 of symmetry of the nanocage. Dipole moment (µo) is a vector product of charge and distance
35
36 among the charged particles. Therefore, high charges and more separation between these charges
37
38
39
results in higher µo values. Our results at LC-BLYP/6-31+G(d) level on superalkali doped B12P12
40
41 nanocages revealed similar trend. Isomers with higher charges on superalkalis and higher
42
43 separation of charges show higher dipole moments. In Li2F@B12P12 series, the highest µo of 6.65D
44
45
is observed for isomer I. The value of µo for isomers II and III is 6.07D and 6.06D, respectively.
46
47
48 Li3O@B12P12 isomers (IV-VII) have µo in the range of 7.48D to 17.85D. Here, the highest µo of
49
50 17.85D is obtained for isomer IV. Among Li4N@A112P12 complexes, isomer IX has the highest
51
52 µo of 12.17D, whereas dipole moments of isomers VIII and X are 4.03 debye and 6.36D,
53
54
55 respectively.
56
57
58 22
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 Polarizability (αo) results revealed that αo (388 au) of B12P12 is slightly increased to 427-434 au for
4
5
6 isomers I and II of Li2F@ B12P12 series but decreased to 317 au for isomer III. For Li3O@ B12P12
7
8 series (IV-VII), αo is increased from 448 to 709 au. For Li4N@ B12P12 series (VIII-X), αo is in the

9
10 range of 464 to 729 au These results indicated alteration of the αo values of the B12P12 cage by the
11
12
13
induction of superalkalis. The introduction of superalkalis dramatically enhances the first
14
15 hyperpolarizability (βo) of the B12P12 nanocage ranging from 6.92×102 au to 3.48×105 au. Among
16
17 Li2F@B12P12 isomers (I-III), isomer III has βo of 3.48×105 au which is followed by isomers I and
18
19
II having βo values of 1.29×103 au and 1.04×103 au, respectively. The Li3O@B12P12 isomers (IV-
20
21
22 VII) showed similar trend of increasing βo as is observed for αo. The highest βo is observed for
23
24 isomer V (3.27×103 au) and then, followed by isomer IV (1.17×103 au). βo values decreased from
25
26 isomer VI (3.10×103 au) to isomer VII (2.44×103 au), respectively. Among the three isomers
27
28
29 (VIII-X) of Li4N@B12P12 complexes, isomer IX has the largest βo value of 1.58×105 au.
30
31 Hyperpolarizability of a system is affected by several factors. One such factor is vertical ionization
32
33 energy (VIE) of the system that can affect hyperpolarizability response, if VIE is the only factor
34
35
36
in determining of hyperpolarizability subsequently monotonic behavior can be predicted. Another
37
38 factor is the interaction distance between superalkali and cage. Shorter the interaction distance
39
40 stronger the interaction between superalkali and nanocage. Therefore, shorter distance leads to
41
42
higher hyperpolarizability and vice versa. If interaction distance is the only factor, then monotonic
43
44
45 increase of hyperpolarizability value by decrease in interaction distance is expected. In our case,
46
47 Li2F@B12P12 series shows monotonic increase in hyperpolarizability with the decrease in vertical
48
49 ionization energies of the isomers suggesting that VIE is the only factor affecting the first
50
51
52 hyperpolarizabilities of this series. Li3O@B12P12 and Li4N@B12P12 series reflect that the above
53
54
55
56
57
58 23
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 discussed both factors are playing their part for increasing the hyperpolarizability response of
4
5
6 respective isomers.
7
8 Table 3: Dipole moment (µo) in debye, polarizability (αo) in au, first hyperpolarizability (βo) in au,

9 oscillator strength (fo), crucial excitation energy (ΔE) in eV and dominated transitions of
10 Li2F@B12P12, Li3O@B12P12 and Li4N@B12P12 complexes.
11
12 fo ΔE Dominated
13 Isomers µo αo βo
transition
14
15 Pure
16 0.00 388.17 0.24
B12P12
17
18 Li2F@B12P12
19
20 I 6.65 434.04 1.29×103 0.050 2.20 HOMO→LUMO
21
22 II 6.07 427.92 1.04×103 0.034 2.11 HOMO→LUMO+1
23
24 III 6.06 316.93 3.48×105 0.037 1.63 HOMO→LUMO+3
25
26
Li3O@B12P12
27
IV 17.85 555.27 1.17×105 0.043 0.71 HOMO→LUMO
28
29 V 7.48 709.63 3.27×105 0.043 1.41 HOMO→LUMO+2
30
31 VI 13.94 454.74 3.10×103 0.025 2.07 HOMO→LUMO
32
33 VII 13.51 448.78 2.44×103 0.038 1.65 HOMO→LUMO
34
35 Li4N@B12P12
36
37 VIII 4.03 663.42 1.58×104 0.155 2.88 HOMO→LUMO+8
38
39 IX 12.17 727.98 1.58×105 0.047 1.39 HOMO→LUMO+2
40
X 6.36 729.79 1.89×104 0.108 1.91 HOMO-1→LUMO
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 24
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3
4
5
6
7
8

9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52 Figure 5: Dependance of first hyperpolarizability βo (au) values on the crucial excitation energies
53 ΔE (eV) of Li2F@B12P12 and Li4N@B12P12 isomers
54
55
56
57
58 25
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3
4
5
6
7
8

9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28 Figure 6: Dependence of first hyperpolarizability βo (au) values on the oscillator strength fo of
29 Li3O@B12P12 isomers
30
31
32
33 According to two level model, hyperpolarizability can be estimated through the following eq:
34
35
36 βo = Δµ × fo / ΔE3
37
38
39
To gain insight into the factor responsible for affecting hyperpolarizability, crucial excited
40
41 energies, oscillator strength and change in dipole moment during crucial excitation are calculated.
42
43 Moreover, the effect of doping position is also studied. In all three series, maximum
44
45
hyperpolarizability is observed for isomers in which superalkali is doped over the center of the
46
47
48 six-membered ring (r6) of the nanocage. Hyperpolarizabilities of isomers III (Li2F@B12P12), V
49
50 (Li3O@B12P12) and IX (Li4N@B12P12) (having superalkali on r6 position) are 3.48×105 au ,
51
52 3.27×105 au and 1.58×105 au respectively. The next higher hyperolarizability is observed for those
53
54
55 systems where dopant (superalkali) resides at Btop position. Hyperpolarizabilities of isomers VIII
56
57
58 26
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 (Li4N@B12P12), IV (Li3O@B12P12) and II (Li2F@B12P12) (having superalkali at Btop position) are
4
5
6 1.58×104 au, 1.17×105 au and 1.04×103 au, respectively.
7
8

9 In literature it has been previously reported that the small transition energy (ΔE) of the crucial
10
11 excited state leads to large first hyperpolarizability βo values. The dominant transitions, their
12
13 corresponding ΔE values and oscillator strengths are given in Table 2. Our calculated results
14
15
16
revealed that, in contrast to the pristine nanocage with large ΔE, the superalkali doped cages exhibit
17
18 much smaller ΔE values of 0.71–2.88 eV, which are comparable to those of 1.24–2.86 eV for the
19
20 Li3O doped Al12N12 electrides.33 Therefore, such small transition energies of crucial excited states
21
22
of these isomers are responsible for the large first hyperpolarizabilities of these superalali doped
23
24
25 B12P12 compounds. As shown in Table 2, for Li2F@B12P12, isomer III exhibits much smaller ΔE
26
27 value 1.63 eV than those of 2.11 eV ‒ 2.20 eV for isomers I and II. Thus, the smaller ΔE of isomer
28
29 III is the main controlling factor for the much larger first hyperpolarizability (βo) value (in
30
31
32 Li2F@B12P12 series) as compared to the other two isomers. A similar trend is observed in
33
34 Li4N@B12P12 series. Isomer IX of Li4N@B12P12 has greater first hyperpolarizability value of
35
36 1.58×105 au as compared with 1.58×104 (VIII) and 1.89×104 (X). Isomer IX has also the smallest
37
38
39
ΔE value in the series therefore, smaller transition energy of the crucial excited state of isomer IX
40
41 is the decisive factor for its large first hyperpolarizability response. In Li3O based series, oscillator
42
43 strength of the crucial excited states become the decisive factor for the large βo values of isomers
44
45
IV and V as compared with VI and VII. From two level method, first hyperpolarizability is directly
46
47
48 proportional to the oscillator strength of the crucial excited state. Isomers IV and V have higher
49
50 oscillator strength of 0.043 as compared with 0.025 (VI) and 0.0386 (VII), hence isomers IV and
51
52 V have higher βo values than VI and VII. In summary, crucial excitation energy is the main
53
54
55
56
57
58 27
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 contributing factor in deciding the first hyperpolarizability. However, oscillator strength of crucial
4
5
6 excited states becomes decisive factor in case of Li3O@B12P12 series.
7
8

9 Conclusions
10
11
12 Several strategies have been reported in the literature to design high performance NLO materials.
13
14
15 A relatively less explored strategy is doping of inorganic systems with superalkali units. This
16
17 research aimed at exploring the potential of superalkali (Li2F, Li3O and Li4N) doping on the non-
18
19 linear optical response of boron phosphide nanocages. The formed nanocage complexes are quite
20
21
22
stable as evident from their calculated binding energies. For all the doped superalkalis, the EH-L
23
24 gaps are reduced significantly. Besides EH-L gaps, hyperpolarizabilities of the considered structures
25
26 are increased up to several orders of magnitude. For example, the highest hyperpolarizability
27
28
(3.5×105 au) is observed for isomer (III) of Li2F@B12P12. The isomer III has the lowest EH-L gap
29
30
31 of 1.46 eV among three isomers (I-III) of Li2F@B12P12. Moreover, it is observed that Li2F gives
32
33 better hyperpolarizability enhancement with B12P12 nanocage as compared to Li3O and Li4N. This
34
35 study will be advantageous for promoting the potential applications of the super alkalis doped
36
37
38 B12P12 based nanostructures. These newly designed excess electron systems and electrides (VIII
39
40 and X) can be used in electronic nanodevices and high-performance nonlinear optical materials
41
42 with good ultraviolet transparency.
43
44
45
46
ACKNOWLEDGEMENT
47
48 This study was financially supported by Higher Education Commission of Pakistan under HEC
49
50 indigenous fellowship to Faizan Ullah (315-19560-2PS3-146) and HEC-NRPU project (7853).
51
52
53 Supplementary information
54
55
56
57
58 28
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 Supplementary data associated with current article can be found online at http://dx.doi.org/
4
5
6
7
8

9 References
10
11
12 1 X. Xu, C. L. Hu, F. Kong, J. H. Zhang, J. G. Mao and J. Sun, Inorg. Chem., 2013, 52,
13
14 5831–5837.
15
16
17 2 O. Maury, L. Viau, K. Sénéchal, B. Corre, J. P. Guégan, T. Renouard, I. Ledoux, J. Zyss

18
19
20
and H. Le Bozec, Chem. - A Eur. J., 2004, 10, 4454–4466.
21
22
23
3 T. G. Zhang, Y. Zhao, I. Asselberghs, A. Persoons, K. Clays and M. J. Therien, J. Am.
24
25 Chem. Soc., 2005, 127, 9710–9720.
26
27
28 4 N. Tancrez, C. Feuvrie, I. Ledoux, J. Zyss, L. Toupet, H. Le Bozec and O. Maury, J. Am.
29
30 Chem. Soc., 2005, 127, 13474–13475.
31
32
33 5 H. L. Sang, R. P. Jo, M. Y. Jeong, M. K. Hwan, S. Li, J. Song, S. Ham, S. J. Jeon and R.
34
35 C. Bong, ChemPhysChem, 2006, 7, 206–212.
36
37
38 6 D. Xiao, F. A. Bulat, W. Yang and D. N. Beratan, Nano Lett., 2008, 8, 2814–2818.
39
40
41 7 C. G. Liu, W. Guan, P. Song, L. K. Yan and Z. M. Su, Inorg. Chem., 2009, 48, 6548–
42
43
44 6554.
45
46
47
8 B. J. Coe, J. Fielden, S. P. Foxon, I. Asselberghs, K. Clays and B. S. Brunschwig, Inorg.
48
49 Chem., 2010, 49, 10718–10726.
50
51
52 9 S. M. LeCours, H. W. Guan, S. G. DiMagno, C. H. Wang and M. J. Therien, J. Am. Chem.
53
54 Soc., 1996, 118, 1497–1503.
55
56
57
58 29
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 10 M. Schulz, S. Tretiak, V. Chernyak and S. Mukamel, J. Am. Chem. Soc., 2000, 122, 452–
4
5
6 459.
7
8

9 11 F. Begum, Y. Namihira, S. M. A. Razzak, S. Kaijage, N. H. Hai, T. Kinjo, K. Miyagi and
10
11 N. Zou, Opt. Laser Technol., 2009, 41, 679–686.
12
13
14 12 I. P. Ilchishin and E. A. Tikhonov, Prog. Quantum Electron., 2015, 41, 1–22.
15
16
17 13 B. Clough, J. Dai and X.-C. Zhang, Mater. Today, 2012, 15, 50–58.
18
19
20 14 Q. Yue, K. Li, F. Kong, J. Zhao and M. Liu, Opt. Commun., 2016, 367, 72–79.
21
22
23 15 R. D. Peterson, B. T. Cunningham and J. E. Andrade, Biosens. Bioelectron., 2014, 56,
24
25 320–327.
26
27
28 16 S. Palmer, S. G. Sokolovski, E. Rafailov and G. Nabi, Clin. Genitourin. Cancer, 2013, 11,
29
30 390–396.
31
32
33 17 M. Noori, M. Soroosh and H. Baghban, Photonics Nanostructures - Fundam. Appl., 2016,
34
35
36 19, 1–11.
37
38
39 18 P. Vennila, M. Govindaraju, G. Venkatesh and C. Kamal, J. Mol. Struct., 2016, 1111,
40
41 151–156.
42
43
44 19 E. Yalçın, S. Achelle, Y. Bayrak, N. Seferoğlu, A. Barsella and Z. Seferoğlu, Tetrahedron
45
46 Lett., 2015, 56, 2586–2589.
47
48
49 20 E. Zarins, A. Tokmakovs, V. Kokars, A. Ozols, P. Augustovs and M. Rutkis, Opt. Mater.
50
51
(Amst)., 2016, 53, 146–154.
52
53
54 21 Y. Maeda, Appl. Surf. Sci., 2008, 254, 6242–6247.
55
56
57
58 30
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 22 S. Chopra, ChemPhysChem, 2015, 16, 1948–1953.
4
5
6 23 S. Priyadarshy, M. J. Therien and D. N. Beratan, J. Am. Chem. Soc., 1996, 118, 1504–
7
8

9 1510.
10
11
12 24 M. Niu, G. Yu, G. Yang, W. Chen, X. Zhao and X. Huang, Inorg. Chem., 2014, 53, 349–
13
14 358.
15
16
17 25 L. Wang, W.-Y. Wang, X.-Y. Fang, C.-L. Zhu and Y.-Q. Qiu, Org. Electron., 2016, 33,
18
19 290–299.
20
21
22 26 J. Beheshtian, A. A. Peyghan and Z. Bagheri, Appl. Surf. Sci., 2012, 259, 631–636.
23
24
25 27 Maria, J. Iqbal and K. Ayub, J. Alloys Compd., 2016, 687, 976–983.
26
27
28 28 K. Ayub, J. Mater. Chem. C, 2016, 4, 10919–10934.
29
30
31 29 J. Beheshtian, Z. Bagheri, M. Kamfiroozi and A. Ahmadi, J. Mol. Model., 2012, 18,
32
33 2653–2658.
34
35
36 30 G. Seifert, P. W. Fowler, D. Mitchell, D. Porezag and T. Frauenheim, Chem. Phys. Lett.,
37
38
39 1997, 268, 352–358.
40
41
42
31 H.-S. Wu, F.-Q. Zhang, X.-H. Xu, C.-J. Zhang and H. Jiao, J. Phys. Chem. A, 2003, 107,
43
44 204–209.
45
46
47 32 E. Shakerzadeh, Z. Biglari and E. Tahmasebi, Chem. Phys. Lett., 2016, 654, 76–80.
48
49
50 33 W.-M. Sun, X.-H. Li, D. Wu, Y. Li, H.-M. He, Z.-R. Li, J.-H. Chen and C.-Y. Li, Dalt.
51
52 Trans., 2016, 45, 7500–7509.
53
54
55 34 W.-M. Sun, L.-T. Fan, Y. Li, J.-Y. Liu, D. Wu and Z.-R. Li, Inorg. Chem., 2014, 53,
56
57
58 31
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 6170–6178.
4
5
6 35 W.-M. Sun, D. Wu, Y. Li and Z.-R. Li, Dalt. Trans., 2014, 43, 486–494.
7
8

9 36 D. C. Pestana and P. P. Power, J. Am. Chem. Soc., 1991, 113, 8426–8437.
10
11
12 37 V. A. Ferreira and H. W. Leite Alves, J. Cryst. Growth, 2008, 310, 3973–3978.
13
14
15 38 A. S. Rad and K. Ayub, J. Mol. Liq., 2017, 238, 303–309.
16
17
18 39 Maria, J. Iqbal, R. Ludwig and K. Ayub, Mater. Res. Bull., 2017, 92, 113–122.
19
20
21 40 S. Munsif, Maria, S. Khan, A. Ali, M. A. Gilani, J. Iqbal, R. Ludwig and K. Ayub, J. Mol.
22
23
Liq., 2018, 271, 51–64.
24
25
26
41 E. Zintl and W. Morawietz, Zeitschrift für Anorg. und Allg. Chemie, 1938, 236, 372–410.
27
28
29 42 C. H. Wu, H. Kudoa) and H. R. Ihle, J. Chem. Phys., 1979, 70, 1815–1820.
30
31
32 43 P. A. Kollman, J. F. Liebman and L. C. Allen, J. Am. Chem. Soc., 1970, 92, 1142–1150.
33
34
35 44 P. K. Pearson, W. J. Hunt, C. F. Bender and H. F. Schaefer, J. Chem. Phys., 1973, 58,
36
37
38 5358–5363.
39
40
41 45 G. L. Gutsev and A. I. Boldyrev, Chem. Phys. Lett., 1982, 92, 262–266.
42
43
44
46 A. Becke, J. Chem. Phys.
45
46
47
47 C. Lee, W. Yang and R. G. Parr, Phys. Rev. B, 1988, 37, 785–789.
48
49
50
48 X. Li, J. Mater. Chem. C, 2018, 6, 7576–7583.
51
52
49 Z. Khajehali and H. R. Shamlouei, Comptes Rendus Chim., 2018, 21, 541–546.
53
54
55
50 E. Shakerzadeh, E. Tahmasebi and Z. Biglari, J. Mol. Liq., 2016, 221, 443–451.
56
57
58 32
59
60
View Article Online
DOI: 10.1039/C9NJ00225A
1
2
3 51 M. Maria, J. Iqbal and K. Ayub, RSC Adv., 2016, 6, 94228–94235.
4
5
6 52 M. B. Oviedo, N. V. Ilawe and B. M. Wong, J. Chem. Theory Comput., 2016, 12, 3593–
7
8

9 3602.
10
11
12 53 M. Torrent-Sucarrat, M. Solà, M. Duran, J. M. Luis and B. Kirtman, J. Chem. Phys., 2004,
13
14 120, 6346–6355.
15
16
17 54 D. Jacquemin, E. A. Perpète, M. Medved’, G. Scalmani, M. J. Frisch, R. Kobayashi and

18
19 C. Adamo, J. Chem. Phys., 2007, 126, 191108.
20
21
22 55 G. E. S. M. J. Frisch, G. W. Trucks, H. B. Schlegel, V. B. M. A. Robb, J. R. Cheeseman,
23
24
G. Scalmani, M. C. B. Mennucci, G. A. Petersson, H. Nakatsuji, G. Z. X. Li, H. P.
25
26
27 Hratchian, A. F. Izmaylov, J. Bloino, J. L. S. Hada and M., .
28
29
30 56 GaussView version 5 and K. R Dennington, T Keith, J Millam - Semichem Inc.: Shawnee
31
32 Mission, 2009.
33
34
35 57 T. Lu and F. Chen, J. Comput. Chem., 2012, 33, 580–592.
36
37
38 58 X.-B. Wang, C.-F. Ding and L.-S. Wang, J. Chem. Phys., 1999, 110, 8217–8220.
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 33
59
60

Ullah 2019

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Ullah 2019

Uploaded by

Copyright:

Available Formats

View Article Online

acceptance, before technical editing, formatting and proof reading.

You can find more information about Accepted Manuscripts in the

Please note that technical editing may introduce minor changes

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

17 are also calculated.

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

17 2 O. Maury, L. Viau, K. Sénéchal, B. Corre, J. P. Guégan, T. Renouard, I. Ledoux, J. Zyss

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

New Journal of Chemistry Accepted Manuscript

17 54 D. Jacquemin, E. A. Perpète, M. Medved’, G. Scalmani, M. J. Frisch, R. Kobayashi and

You might also like