Solvent Effect on the Interaction of C20 and N2H2

Solvent Effect on the Interaction of C20 and N2H2 Solvent effect on the interaction of C20 and N2H2: A theoretical study Reza Ghiasi*,1, Hanieh Alavi2 Abstract: In this work, the interaction of C20 and N2H2 fragment was investigated in the M062X/6-311G(d,p) level of theory in both gas and solution phases. The influence of solvent on the interaction energy, structural parameters, frontier orbital energies and hyperpolarizability of C20†¦N2H2 complex has been explored. The interaction energies obtained with standard method were corrected by basis set superposition error (BSSE) during the geometry optimization for all complexes at the same levels of theory. The thermodynamic properties of the C20†¦N2H2 molecule at vacuum phase and different solvents have been calculated. Keywords: C20 cage, C20†¦N2H2 molecules, Frontier orbitals, solvent effect, hyperpolarizability. Introduction C20 molecule is potentially the smallest fullerene, and its structure has been investigated theoretically and experimentally [1-6]. This molecules has been generated and characterized in the gas phase [7]. Owing to its attractive structure, this ambiguous molecule has been the subject of many theoretical investigations [8, 9]. Fullerenes are considered as promising candidates for basic elements in nanoscale devices, and several examples of fullerene-based devices have been already investigated both experimentally and theoretically [10, 11]. Modification of C20 is a matter of general interest for experimentalists as well theoreticians to look into the structural as well as electronic properties. As a recent research, for instant, structure and properties of fullerene C20 and its derivatives C20(C2H2)n and C20(C2H4)n (n=1–4) have been studied [12]. These calculations showed that the most stable fullerene C20 and its derivatives C20(C2H2)n and C20(C2H4)n (n=1–3) reveal sig nificant aromaticity, while C20(C2H2)4 and C20(C2H4)4 have no spherical aromaticity. Also, heteroatom impacts on structure, stability and aromaticity of XnC20-n fullerenes have been explored [13]. The interaction of C20 with N2X2 (X=H, F, Cl, Br, Me) have been investigated theoretically [14]. Structure, aromaticity, frontier orbital analysis and the natural bond analysis of C20†¦N2X2 complexes have been explored, and the influence of the basis set and methods on the structure and interaction energies of these complexes have been explored. In the present work, extensive theoretical calculations on fullerene C20 and their interactions with N2H2 have been performed in both gas and solution phases. The Structure, frontier orbital analysis and hyperpolarizability of the C20†¦N2H2 have been explored. We also discuss the influence of the solvent on the structure properties of C20†¦N2H2 molecule. Computational Methods All calculations were carried out with the Gaussian 09 suite of program [15]. The calculations of systems contain C, and N described by the standard 6-311G(d,p) basis set [16-19]. Geometry optimization was performed utilizing with the hybrid functional of Truhlar and Zhao (M062X) [20]. A vibrational analysis was performed at each stationary point found, that confirm its identity as an energy minimum. The interaction energy, IE, can be evaluated from the difference between energy of the complex and sum of the energies of the C20 and N2H2: I.E = E(complex) – [E (C20)+ E(N2H2)] The calculated interaction energies were corrected for basis set superposition errors (BSSE), which were computed for all calculations using the counterpoise correction method of Boys and Bernardi [21]. Geometries were optimized at this level of theory without any symmetry constraints followed by the calculations of the first order hyperpolarizabilities. The total static first hyperpolarizability à ¯Ã‚ Ã‚ ¢ was obtained from the following relation: upon calculating the individual static components Due to the Kleinman symmetry [22]: à ¯Ã‚ Ã‚ ¢xyy = à ¯Ã‚ Ã‚ ¢ yxy = à ¯Ã‚ Ã‚ ¢ yyx ; à ¯Ã‚ Ã‚ ¢yyz = à ¯Ã‚ Ã‚ ¢ yzy = à ¯Ã‚ Ã‚ ¢ zyy,†¦ one finally obtains the equation that has been employed: We have studied the solvation effects by using self-consistent reaction field (SCRF) approach, in particular using the polarizable continuum model (PCM) [23]. Using this method, the geometry of the studied complex was re-optimized and the hyperpolarizability was calculated by the same functionals and basis sets. Results and discussion Energetic The computed interaction energies (I.E) and the corrected interaction energies (I.E corrected) for the C20†¦N2H2 complex (Figure 1) in gas phase and various solvents have been gathered in Table 1. It can be expected interaction between C20 and N2H2 increases in the presence of more polar solvents. Figure 2 presents a good correlation between interaction energies values and dielectric constants of solvents. On the other hand, the comparison of interaction energy value in gas phase and solution phase show more interaction between C20 and N2H2 in solution phase. Thermochemical Analysis Thermochemical analysis is studied for all complexes. The values of à ¯Ã‚ Ã¢â‚¬Å¾H, à ¯Ã‚ Ã¢â‚¬Å¾G and K are reported in Table 2 in which the individual terms are referred to a temperature of 298 K. The reaction can be considered as: C20 + N2H2à ¯Ã¢â‚¬Å¡Ã‚ ® C20†¦N2H2 As can be verified, the à ¯Ã‚ Ã¢â‚¬Å¾G values increase in solution phase. The equilibrium constants of the all complexes are given in Table 2. This shows that the equilibrium constant is most vacuum phase. Dipole moments The dipole moments of C20†¦N2H2 complex in gas phase and different solvents have been listed in Table 3. As seen in Table 3, C20†¦N2H2 complex has less dipole moment in gas phase. In the solution phase, dipole moments increase with increasing of polarity of the solvents. Also, these values show a good relationship with interaction energies values (Figure 3). Polarizability The isotropic and anisotropic polarizability values of C20†¦N2H2 complex in gas phase and different solvents have been gathered in Table 3. As seen in Table 3, C20†¦N2H2 complex has less polarizability in gas phase. There is good correlation between isotropic polarzability values and dielectric constants of solvent (R2=0.948). Bond distances The NN and C..N bond distances of C20†¦N2H2 complex in gas phase and different solvents have been collected in Table 1. As seen from Table 1, the bond lengths increase in solution phase. There is minor dependence between bond distances and dielectric constants values. The comparison NN bond distances of free N2H2 and complexed molecule show the rising of this bond in C20†¦N2H2 complex. Molecular orbital analysis The energies of the frontier orbitals (HOMO, LUMO) along with the corresponding HOMO–LUMO energy gaps for of C20†¦N2H2 complex in gas phase and different solvents are given in Table 4. Inclusion of solvation effects leads also to changes on the molecular orbital energies (Table 4). In solution, HOMO and LUMO are destabilized, with respect to the corresponding values in vacuum. Also, HOMO-LUMO gap and hardness of C20†¦N2H2 complex in solution phase is more than gas phase. A good relationship between HOMO-LUMO gap and polarity of solvents (R2=0.954). The variations in this property may be illustrated by considering the fact that neutral or charged species enhance their effective radii in solution phase. This signifies that the electrostatic potential q/r will forever diminish from gas phase to solution phase. As a result, solvated species will reduce their effective hardness and subsequently become softer in the solution phase [24]. On the other hand, when the interaction between C20 and N2H2 increases, then the most hardness values have observed. There is a good linear correlation between interaction energies and hardness values (R2=0.949). Electrophilic charge transfer (ECT) of C20†¦N2H2 complex in gas and various solvents has been reported in Table 4. ECT is defined as the difference between à ¯Ã‚ Ã¢â‚¬Å¾Nmax values of interacting molecules: ECT = à ¯Ã‚ Ã¢â‚¬Å¾Nmax(N2H2) à ¯Ã‚ Ã¢â‚¬Å¾Nmax(C20) In this equation à ¯Ã‚ Ã¢â‚¬Å¾Nmax is defined as: The positive values of ECT reveal charge flow from C20 to N2H2. On the other hand, these values show the decreasing of charge transfer with increasing of solvent polarity. Hyperpolarizability It is illustrated that solvent polarity participate an important role on the first hyperpolarizabilities in dipolar molecules. The à ¯Ã‚ Ã‚ ¢tot , à ¯Ã‚ Ã‚ ¢x, à ¯Ã‚ Ã‚ ¢y, à ¯Ã‚ Ã‚ ¢z values of C20†¦N2H2 complex in different solvents have been listed in Table 5. These values indicate à ¯Ã‚ Ã‚ ¢tot values decrease from vacuum to solution phase (à ¯Ã‚ Ã‚ ¢total=0.0 for C20). The dependence of the first hyperpolarizability of the studied compound both on the dielectric constant of the media and the Onsager function has been investigated [25]. Figure 4 is typical for a dipolar reaction field interaction in the salvation process [25-28]. Therefore, the electronic reorganization in solution for C20†¦N2H2 complex acts an important effect on the resulting first hyperpolarizabilities. Conclusion: We showed in paper: The interaction energies values increase from vacuum to different solvents. In solution, HOMO and LUMO energies, hardness and chemical potential values are increased, with respect to the corresponding values in vacuum. On the other hand, electrophilicty values have been decreased in solution phase. The largest à ¯Ã‚ Ã‚ ¢tot values have been found in more polartity, and these values increase from vacuum to different solvents. References: [1]J. C. Grossman, L. Mitas, K. Raghavachari, Phys. Rev. Lett., 750, 3870 (1995). [2]E. J. Bylaska, P. R. Taylor, R. Kawai, J. H. Weare, J. Phys. Chem. A, 100, 6966 (1996). [3]R. Taylor, E. Bylaska, J. H. Weare, R. Kawai, Chem. Phys. Lett, 235, 558 (1995). [4]Z. Wang, P. Day, R. Pachte, Chem. Phys. Lett., 248, 121 (1996). [5]M. L. M. Jan, J. El-Yazal, J. Francois, Chem. Phys. Lett. , 248, 345 (1996). [6]S. Sokolova, A. Luchow, J. B. Anderson, Chem. Phys. Lett. , 323, 229 (2000). [7]H. Prinzbach, A. Weiler, P. Landenberger, F. Wahl, J. Worth, L. T. Scott, M. D. Gelmont, D. Olevano, B. V. Issendorff, Nature, 60, 407 (2000). [8]J. Luo, L. M. Peng, Z. Q. Xue, J. L. Wu, J. Chem. Phys, 120, 7998 (2004). [9]Z. Chen, T. Heine, H. Jiao, A. Hirsch, W. Thiel, P. v. R. Schleyer, Chem. Eur. J. , 10, 963 (2004). [10]J. Taylor, H. Guo, J. Wang, Phys. Rev. B 63, 121104 (2001). [11]D. Zeng, H. Wang, B. Wang, J. G. Hou, Appl. Phys. Lett, 77, 3595 (2000). [12]C. Zhanga, W. Sun, Z. Caob, J. Chem. Physics, 126, 144306 (2007). [13]M. Z. Kassaee, F. Buazar, M. Koohi, Journal of Molecular Structure: THEOCHEM, 940, 19 (2010). [14]R. Ghiasi, M. Z. Fashami, J. Theo.Comput. Chem (2014). [15]M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalman, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Revision A.02 ed., Gaussian, Inc., Wallingford CT, 2009. [16]R. Krishnan, J. S. Binkley, R. Seeger, J. A. Pople, J. Chem. Phys. , 72, 650 (1980). [17]A. J. H. Wachters, J. Chem. Phys., 52, 1033 (1970). [18]P. J. Hay, J. Chem. Phys. , 66, 4377 (1977). [19]A. D. McLean, G. S. Chandler, J. Chem. Phys., 72, 5639 (1980). [20]Y. Zhao, D. G. Truhla, J. Phys. Chem, 110, 5121 (2006). [21]S. F. Boys, F. Bernardi, Mol. Phys., 19, 553 (1970). [22]D. A. Keleiman, Phy. Rev., 126, 1977 (1962). [23]J. Tomasi, B. Mennucci, R. Cammi, Chem. Rev., 105, 2999- (2005). [24]R. Pearson, J. Am. Chem. Soc. , 108, 6109 (1986). [25]L. Onsager, J. Am. Chem. Soc., 58, 1486 (1936). [26]K. Clays, A. Persoons, Phys. Rev. Lett. , 66, 2980 (1991). [27]H. Lee, S.-Y. An, M. Cho, J. Phys. Chem. B, 103, 4992 (1999). [28]P. C. Ray, J. Leszczynski, Chem. Phys. Lett., 399, 162 (2004). 1

Comparing and contrasting Bandura’s cognitive theory Essay

Introduction Perhaps there are as many differences as there are similarities between the ideas expressed in Bandura’s Cognitive Theory and Beck’s Cognitive Theory. Many similarities exist between the two theories because they are both based on the study of human behavior and personality. However, the ideas expressed and mechanisms used in analysis confer some discord between the two theories. It is evident that no two persons in the world would have exclusively similar thoughts about a phenomenon; hence, differences are always abound. Since studies in similar fields are usually related in a way, prevalence of similarities should not occur as a surprise. For example, the fact that behavior is affected by, among other things, the environment, is embraced in the detail of both theories. The two theorists are also of common opinion that negative thoughts are likely to trigger negative behavior and dysfunction in many activities. For example, Bandura’s theory highlights that people with high opinions about themselves are usually better performers in many activities than those who weigh themselves on a lower scale. In the same way, Beck’s theory is emphatic of the point that negative thoughts in people lead such people to have low opinion of themselves and evaluate themselves negatively. Bandura’s Cognitive Theory and Beck’s Cognitive Theory both view the environment as a determinant of personality and behavior. While Bandura (1976) used â€Å"environmental factors† in his triad, Beck (1976) showed that the â€Å"world† (in reference to the environment) is one of the factors that shape a person’s behavior, attitudes and perceptions about various phenomena. Both theorists agree that the environment acts together with other factors to shape a person’s character and behavior. For instance, Bandura (1986) observed that aggressive behavior in adolescents is caused by the environment, but the behavior as well creates an environment. Bandura referred to such a relationship as reciprocal determinism. On the other hand, Beck (1976) noted that the world shapes a persons character since a person acts in accordance with what is happening in the general world. Disparities in Bandura’s and Beck’s theories are evident right from the beginning of the model. While there is a similarity of the use of a triad, the constituents of the triads are the source of dissonance. This is in addition to many other instances in the illustration of the applications of the two models. This paper gives an analysis of the similarities and differences in the two theories and the implications or causes of such scenario. Moreover, the paper will highlight the key areas where similarities as well as differences occur between the two theories.

Charlotte Perkins Gilman, Simone De Beauvoir, and Virginia...

Many philosophers have argued that freedom should be applied to men in society. They argue that men should have both physical freedom and the liberty to express themselves. However, not many philosophers take into account the freedom and equality that women should have by nature. In the women’s case, equality is a necessary condition of freedom. In the works by women philosophers Charlotte Perkins Gilman, Simone De Beauvoir, and Virginia Woolf, an analysis on their works shows that these authors believe equality is absolutely a necessary condition of freedom for women. Due to the presence of and dependence on men, women are deprived from using their freedom to expand their knowledge, reason and their social standing. Thus, women don’t†¦show more content†¦She believes this inequality deprives women to be able to use their reason and freedom to their advantage. Gilman also says, â€Å"her confinement to the four walls of the house, have done great execution of course, in limiting her ideas, her information, her thought processes, and power of judgment†(Gilman 66). This confinement of women into the position of housewife is a way in which men deprive women of using their freedom to achieve the greatest potential they can. Women might be free physically but they are not free mentally. After women submit into marriage, they are enclosed and put into bubbles in which they are not allowed to think anything that men do not approve of that might be a disadvantage to them. Women owe everything they have to men and in return women are forced to pay the men back through domestic labor, enslaving themselves to male dominance. Men deprive women from the freedom to decide and they direct all the domestic activities women perform. Because of this system, the unequal distribution of power has not allowed women to have power over themselves and instead are enslaved in a cage and not free to exercise and expand their knowledge and reason. In addition to Gilman’s argument about marriage inequality she also goes on to say that women should change their cultural identities and take control of themselves by

His Mistress Going To Bed By Donne - 1272 Words

The Laws of Seduction On the surface, Donne’s â€Å"To His Mistress Going to Bed† seems like a simple request to admire and charm his mistress into sex. However, his impressive background of theology, cosmology and law is embedded in a subtle fashion which causes the poem to be much more elaborate than what first meets the eye. Donne suffered a few losses during his years including the loss of jobs, imprisonment, still born children, and the eventual death of his wife. If his poetry is any attempt to use wit and mastery to make up for his social shortcomings, this poem certainly aids in redirecting his readers. In â€Å"To His Mistress Going to Bed†, Donne incorporates diction, allusions, similes and metaphors surrounding sex, religion and law in†¦show more content†¦If his wit and intelligence is not enough to convince his companion, he also compares her girdle to the glistering of â€Å"heaven’s zone† (5). He then takes it a step further and declares that her girdle encompasses a far fairer world than heaven’s zone itself (6). The exaggeration of the comparison between the sparkle of jewels on her girdle and the radiance of heaven’s zodiac emphasizes the magnitude of captivation that the speaker claims in his continued efforts to sleep with her. Donne’s inclusion of religion and spirituality both reinforces his broad scope of knowledge and downplays the animalistic perception surrounding sex. â€Å"Bringest with thee a heaven like Mahomet’s paradise† alludes to Donne’s knowledge of the Quran belief system, while providing another smooth comparison of the speaker’s desires with his mistress (20-21). He also compares the white robe she wears in the poem to the robes â€Å"†¦heaven’s angels used to be/ Received by men†¦Ã¢â‚¬  in (19-20). His combination of erotic language and association with the alleged heaven-like, virgin angel’s in Mahomet’s paradise aids in softening his approach to woo the mistress (cite footnote 3 here). Metaphors that compare their â€Å"soft bed† to a â€Å"hallowed temple† compliment the religious associations while also adding a sacred tone to his speech (18). His comparison of her to angels, heaven and paradise also evo kes the supernatural type ofShow MoreRelatedComparing To his Coy Mistress by Andrew Marvell and To his Mistress Going to Bed by John Donne1511 Words   |  7 PagesComparing To his Coy Mistress by Andrew Marvell and To his Mistress Going to Bed by John Donne In recent times I have compared and contrasted two pieces of love poetry, both of which are exceptionally lyrical and full of intellectual language that bring the poems alive with elaborated metaphors that compare dissimilar things, as they Inare equally, yet somehow individually both metaphysical poems. The first of these poems that I comprehended was To his Coy Mistress; (writtenRead MoreA Comparison of ‘To His Coy Mistress’ by Andrew Marvell and ‘To His Mistress Going to Bed’ by John Donne2064 Words   |  9 PagesA Comparison of ‘To His Coy Mistress’ by Andrew Marvell and ‘To His Mistress Going to Bed’ by John Donne ‘To His Coy Mistress’ and ‘To His Mistress Going to Bed’ are both poems about men seducing women. They centre around sex rather than love or romance. Sixteenth and seventeenth century attitudes to love and relationships were much stricter going as far as wealthy people asking their perspective lovers to court them via love poem or letter. Though this has changed fromRead MoreJohn Donne to his mistress going to bed comparative discussion with Courtly love or woman as thing and Unbearable Weight1724 Words   |  7 PagesDonne’s poem ‘To His Mistress Going to Bed’1 appears on the surface to be a poem celebrating the beauty of the female body and the joys of sex. However it is through a closer reading that we see that this poem is in fact not celebrating the woman at all, rather she becomes an object through which the speaker can achieve his desire. By looking at Slavoj Ã… ½iÃ… ¾ek’s essay ‘Courtly Love, or, Woman as Thing’2 and Susan Bordo’s ‘Unbearable Weight’ 3 we can see how Donne represents the mistress of this poem toRead More To His Coy Mistress Essay1227 Words   |  5 PagesTo His Coy Mistress Compare and Contrast â€Å"To His Coy Mistress† By John Donne. â€Å"To His Coy Mistress† and â€Å" To His Mistress Going to bed† are two poems that feature â€Å"carpe diem†; they are also written by two of the most well known metaphysical poets. Andrew Marvell, the author of â€Å"To His Coy Mistress† and John Donne, the writer of â€Å"To His Mistress Going To Bed†. Both poems were written through the 16th and 17th Century, where love and sex were describe as two different things. 16th and 17th Read MoreEssay on Romantic Contradiction in the Poetry of John Donne1010 Words   |  5 Pagesthe Poetry of John Donne John Donnes poem Elegy 19: To His Mistress Going to Bed is closely related to The Sun Rising in its treatment of love, lust, and togetherness. Both discuss and argue different stances on the same topics, but are united by their language and development. The structure of Elegy 19 and use of poetic techniques relate it directly and indirectly to The Sun Rising. In Elegy 19, there are forty-eight lines of adoration of the mistress of the title; this poemRead MoreEssay on John Donne1928 Words   |  8 PagesJohn Donne John Donne had a rich life full of travel, women and religion. Donne was born in 1572 on Bread Street in London. The family was Roman Catholic which was dangerous during this time when Catholicism was being abolished and protestant was taking over. Donne’s farther was an iron monger who died in 1576. At 11 Donne and his younger brother went to university and studied there for three years then he went to Cambridge for a further three years. He left without any degrees becauseRead MoreJohn Donne Love Poetry1442 Words   |  6 Pagesin his prose book â€Å"The Dyers Hand and Other Essays† suggests â€Å"What makes it difficult for a poet not to tell lies is that, in poetry, all facts and all beliefs cease to be true or false and become interesting possibilities†¦It may not, perhaps, be absolutely necessary that he believe it, but it is certainly necessary that his emotions be deeply involved, and this they can never be unless, as a man, he takes it more seriously than as a mere poetic convenience.† It is Donne’s sensibility and his personalRead More To His Mistress Going to Bed, Good Morrow, Corinnas Going A-Maying, and To His Coy Mistress2411 Words   |  10 Pages Seduction in To His Mistress Going to Bed, Good Morrow, Corinnas Going A- Maying, and To His Coy Mistress Throughout time, one of the greatest challenges mankind has faced is the sexual conquest of womankind. In many cultures today, this challenge has evolved into an intricate courting process that often involves buying the woman flowers, gifts, and meals to persuade her to have sex. Another device that a man might use to seduce a woman is poetryRead More To his Coy Mistress by Andrew Marvell and The Flea by John Donne1987 Words   |  8 PagesTo his Coy Mistress by Andrew Marvell and The Flea by John Donne Two of the poems in Best Words are seduction poems, rather than love poems. These are To his coy mistress by Andrew Marvell and The Flea by John Donne. Compare these two poems by analysing: -  · Each poets intention  · Form of the poem  · Language used in the poem  · Your reaction to the unromantic poems. ‘Let me not to the marriage of true minders/Admit impediments, love is not love’, is one of many famous love sonnetsRead MoreEssay on The Flea by John Donne2357 Words   |  10 PagesThe Flea by John Donne â€Å"The Flea†, a witty poem of seduction and conceit, taken from John Donne’s â€Å"Songs and Sonets† is the poem that I have chosen to compare to â€Å"Song†, another poem of John Donne’s where he is passionately pleading with his wife not to be disheartened about his departure abroad. Both poems which belong to â€Å" Songs and Sonets†, written around the time of the 16th century, show that their title suggests they are both short poems, following the traditional form of a sonnet