Room-temperature-superconducting Tc driven by electron correlation

Room-temperature-superconducting Tc measured by high pressure in hydrides can be theoretically explained by a Brinkman–Rice (BR)–Bardeen–Cooper–Schrieffer (BCS) Tc combining both the generalized BCS Tc and the diverging effective mass, m*/m = 1/(1 − (U/Uc)2), with the on-site Coulomb interaction U in the BR picture. A transition from U in a correlated metal of the normal state to Uc in the superconducting state can lead to superconductivity, which can be caused by volume contraction induced by high pressure or low temperature.

R oom -te mpe rat ure -su per conducting T c driven by electron correlation

Hyun-Tak Kim
Room-temperature-superconducting T c measured by high pressure in hydrides can be theoretically explained by a Brinkman-Rice (BR)-Bardeen-Cooper-Schrieffer (BCS) T c combining both the generalized BCS T c and the diverging effective mass, m*/m = 1/(1 − (U/U c ) 2 ), with the on-site Coulomb interaction U in the BR picture. A transition from U in a correlated metal of the normal state to U c in the superconducting state can lead to superconductivity, which can be caused by volume contraction induced by high pressure or low temperature.
Since 1911, Onnes's discovery of the superconductivity phenomenon of zero resistance in Hg, the continues efforts have been made to create and find a room temperature superconductor possessing an intriguing scientific and technological potential. Ashcroft predicted that the room-temperature T c can be achieved for hydrogen solid metal with an extremely high Debye temperature given as inversely proportional to root hydrogen mass ω Debye ∝ 1/ M Hydrogen−mass 1 . In 1935, Wigner and Huntington claimed that at a pressure of 25 gigapascals (GPa), solid molecular hydrogen would turn into a metal 2 . Silvera and Dias managed to turn hydrogen to metallic at a pressure of 495 GPa, well beyond the 360 GPa of Earth's core 3 . In 1970, Satterthwaite & Toepke first observed superconductivity of T c ≈ 8.05 ~ 8.35 K in the hydrides and deuterides of thorium with H-or D-to-metal atom ratios of 3.60-3.65 4 . They asserted that these materials are apparently type-II superconductors with H c2 of the order of 25-30 kg at 1.1 K 4 . In 2008, a hydride, SiH 4 , revealed the metallic characteristic at 50 GPa and superconductivity of T c ≈ 17 K at 100 GPa 5 .
From 2005, the high T c was observed at 203 K and 150 GPa for H 3 S 6 , at 250 ~ 260 K and 180-200 GPa for LaH 10 7 , at 287 K and 274 GPa for a H-S-C compound 8 , and over onset 500 K for a LaH 10 superhydride 9 . The first-principle calculations revealed a large density of states at the Fermi energy 10,11 . The isotope shifts of α = 0.50 ~ 0.35 (T c ≈ M −α ) measured for D 2 S 6 , α = 0.465 calculated by the first-principle approximation for LaD 10 12 , and α = 0.4 experimentally evaluated for YD 6 13 , suggested that the electron-phonon interaction such as the BCS (Bardeen-Cooper-Schrieffer) s-wave superconductor 6,12 is the pairing mechanism of superconductivity.
A particular feature of hydrides is a T c divergence observed above a transition pressure, P transition , which leads to room-temperature superconductivity 8,14,15 , as shown in Fig. 1a. The T c rise with the applied pressure is gradual below P transition and sharp over P transition . The gradual T c rise is attributed to the small increase of the metal phase in the coexistence state of metal and insulator phases, while the sharp T c rise results from the nearly single metal phase formed by the first-order insulator-metal transition (IMT) 16,17 ; this is due to the percolation phenomenon. The IMT is not accompanied by any structural phase transition 6,18 . The IMT-percolation layout is shown in Fig. 1, which indicates that hydrides are the first-order IMT material undergoing percolation with increasing doping (or band filling), such as VO 2 with inhomogeneity in the IMT process. This process implies hydrides are correlated materials. The first-order phenomenon has also been previously reported 19 .
Regarding the room-temperature T c , it may not be explained by the weak coupling BCS T c with the electron-phonon coupling constant, λ ≤ 0.435, which describes the low-T c superconductivity 20 . As an alternative, the strong-coupling McMillan T c 21 and the Allen-Dynes T c 22 without a restriction of the magnitude of λ have been suggested, although a max λ Migdal ≡ N(0)V Migdal ≤ 1.5 has been given 19 . They are based on the Eliashberg formalism utilizing the increase in the Cooper-pair potential V Migdal with strong coupling 23 and not the density of states N(0), the screened Coulomb repulsive potential μ, and the double potential well structure. μ depends on the number of carriers and is smaller in magnitude than the on-site short range repulsive Coulomb interaction, U. However, in the case of hydrides with a high Debye energy (ћω), due to the increase in the retarded Coulomb pseudo-potential, μ * = μ/(1 + μln(E F /ћω)) derived in conditions of λ << 1 and μ << 1 24 , caused by a large deviation of ln(E F /ћω) > 1 in μ * , the exponential parts in the McMillan T c and the Allen-Dynes T c become much smaller www.nature.com/scientificreports/ than that obtained in BCS theory (see "Methods"). Although Allen-Dynes T c , with ћω log /1.2, an average of the phonon energy, different from ћω/1.45 as the prefactor of the McMillan T c , is accurate at a small μ * value 25 , the T c declines. This is due to the decrease in the exponential part in the T c formula which is attributed to an increased value of μ * caused by a large Debye energy (see "Methods") 26 . A comparison of the BCS T c and the T c s based on the Eliashberg formalism is shown 25 . Furthermore, an T c ∝ exp [− 1/(λ-μ * )] derived in λ << 1 and μ * << 1 on the basis of Elisahberg formalism 24 does not rise to room temperature, because λ′ = λ − μ * decreases with increasing μ * for hydrides. Therefore, the T c s do not reach room temperature. Subsequently, Migdal's theory 23 revealed that the increase in λ Migdal , as strong coupling, results in the decrease in sound velocity proportional to the Debye energy, leading to the decrease in T c . This finding indicates that a strong coupled model cannot explain the high T c . Moreover, an exceedingly large λ = 6.2 was evaluated from experimental values using the McMillan T c for YH 6 27 , which is much larger than the calculated value (λ = 1.71 ~ 2.24) 13 . The Eliashberg formalism does not fit the isotope effect 11 . Bogoliubov calculated the electron-phonon interaction by introducing the screened Coulomb repulsive interaction between electrons 28 , concluding that the screened Coulomb interaction plays little role in inducing superconductivity because the magnitude of the electron-phonon interaction is largely reduced by the Coulomb interaction. Thus, no theory is available to explain the high T c . To enhance the T c , the magnitude of density of states N(0) rather than the electron-phonon interaction should be increased. A BCS-based T c that uses large N(0) as a function of band filling is needed.
In this report, we confirm the rise in T c to room temperature by demonstrating the T c divergence over T ransition using a proposed BCS theory supported by the Brinkman-Rice picture 29 , with the diverging effective mass contributing to the density of states for a strongly correlated metal with U/U c = κ BR ≈ 1 (≠ 1). We reveal a fundamental cause of the electron-phonon interaction for superconductivity. The cause has remained obscure since the discovery of Onnes's superconductivity in 1911, despite the development of BCS theory. in BCS theory, the energy gap of the Cooper pair and T c need to be generalized. We find a generalized energy gap of the Cooper pair, a generalized T c , and a generalized coupling constant between the energy gap and T c without any restrictions in BCS theory. The energy gap, ε g = Δ, of Eq. (2.40) in BCS theory 20 is derived using sinh(x) = (e x − e −x )/2 as follows: where ћω is the Debye's phonon vibration energy, λ BCS = N(0)V e-ph is the electron-phonon coupling constant when the electron correlation is not considered, N(0) is the density of Bloch states of one spin per unit energy at the Fermi surface E F , and V e-ph is a constant matrix element of the electron-phonon pair energy. Equation (1), satisfied with λ BCS ≠ ∞, has a divergence in the denominator and has no restrictions on the magnitude of λ BCS . In the case of λ BCS ≤ 0.435, (which is the weak coupling limit confirmed by this author), Eq. (1) 30 . Here, to be the maximum T c in Eq. (2), z should be ∞ in the function of C(z), after which coth(z) = 1 and max 13 are obtained, where γ ≈ 0.577 is the Euler constant. The derivation of Eq. (2) is given in the Supplementary Information. The T c decreases with a decreasing z below z = 3, as shown in Fig. 1b. This phenomenon deviates from the limitation of the weak coupling BCS theory in which T c is defined as over z = 3.
Moreover, the relation between the generalized energy gap Δ in Eq. (1) and the generalized T c in Eq. (3) is given as The coupling constant, b, rapidly increases below z = 3 irrespective of a value of λ BCS , as shown in Fig. 1(b), and it also increases over λ BCS ≈ 0.435. Superconducting T c driven by electron correlation. High-T c superconductors with z < 3 have the T c enhancement. In contrast, the T c in Eq. (3) decreases, as shown in Fig. 1b. This means that Eq. (3) does not account for the increased T c . Thus, to raise T c , as a new concept, we assume the existence of the on-site Coulomb repulsive interaction (or correlation), U, between free electrons at the Fermi surface in a strongly correlated The assumption is based on the firstprinciple calculations 10,11 , the divergence of the effective mass near the optimal doping [31][32][33] , and a suggestion that the strong correlation needs to be introduced 34 . The mass of carriers (quasiparticles) in the correlated metal is much heavier than that in the metal of BCS theory. As a result, the kinetic energy, ε k , of the carriers, as expressed as The kinetic energy does not contribute to the electron-phonon interaction 35 . Although ε BCS is replaced by ε k , the Hamiltonian and the T c -formula form in BCS theory are not changed 35 . The BCS T c equation was also solved by the Green function method 36 . The effect of the heavy mass of the carriers is independently compensated in the density of states for the T c formula. Additionally, the inhomogeneity effect intrinsically appearing in the strongly correlated materials needs to be considered, which has been previously developed 32,33 .
Then, Eq. (3) is newly defined as follows; (1) where Θ D * = ρ 1/3 Θ D is an effective Debye temperature, λ * ≡ Aλ BCS is an effective coupling constant, and A ≡ N(0) * /N(0) = ρ 1/3 /(1 − κ BR 2 ρ 4 ) is a ratio of an effective 3D-density of states, N(0) * ∝ m * n 1/3 , at E F . In the two dimensional case, N(0) * ∝ m * is given. The λ BCS is a constant, which is indefinite and must be extremely small. An effective mass of quasiparticles is given as m * /m ≡ 1/(1 − (U/U c ) 2 ) = 1/(1 − ρ 4 ) from U/U c = κ BR ρ 2 and, the correlation strength, 0 < κ BR < 1 and, here, κ BR ≈1 (or 0.999…, not one) 29,32,33 (Fig. 2a). A carrier density at E F , n = ρn tot , is the extent of the metal region, 0 < ρ = n/n tot < 1 is the band-filling factor (or the normalized carrier density), and n tot  32,33 , and the ratio A. In the inset, the layout of the inhomogeneous mixed phase with a correlated metal (κ BR ≡ U/U c ≈ 1 (≠ 1)) and insulator phases in the measurement region is also depicted. (b) The λ BCS dependence of the BR-BCS T c is shown. Here, the Θ D = 1250 K in Eq. (6) was used. As λ BCS increases, T c increases at a constant ρ. At a constant T c , as λ BCS increases, ρ decreases but λ * does not change. www.nature.com/scientificreports/ is the number of all atoms in the measurement region 32,33 . ρ can be obtained from the Hall-effect experiment or the integral of the optical conductivity. ρ 1/3 in Θ D * comes from the number of phonons in the phonon energy of lattices in the superconducting region (or metal phase over T c ) (inset in Fig. 2a). m * = m/(1 − ρ 4 ) is obtained by applying an effective Coulomb energy, U/U c = κ BR ρ 2 and κ BR ≈ 1, deduced in an inhomogeneous system to the Brinkman-Rice(BR) picture explaining the correlation effect in correlated metals formed by the impuritydriven IMT [37][38][39] , which is an average effect (or measurement effect) of the true effective mass, m * = m/(1 − κ BR 2 ) at ρ = 1 32,33 . The λ BCS dependence of T c,BR-BCS is shown in Fig. 2b. A large T c change occurs in a small ρ variation near the half-filling ρ ≈ 1, confirming the presence of a divergence in the T c formula. Moreover, when the λ BCS value is slightly changed, ρ also varies. At a constant T c , as λ BCS increases, ρ decreases, but λ * does not change. Moreover, the physical meaning of the T c,BR-BCS of Eq. (6) indicates an experimentally measured local T c in the measurement region, which is an average (measurement effect) of the large intrinsic true T c of Eq. (7) expressed by the true effective mass, m * = m/(1 − κ BR 2 ), at ρ ≈ 1 in the BR picture 29 (see Supplementary Information). The intrinsic true T c of Eq. (7) is given as a function of κ BR by applying ρ ≈ 1 into Eq. (6), which has a large diverging value near κ BR = 1. The true T c is constant determined at a given κ BR ≈ 1 (≠ 1). The observed energy gap is obtained by replacing ћω and λ BCS in Eq. (1) with k B Θ D * and λ * , respectively. The coupling constant, b, is determined by substituting λ BCS in Eq. (4) with λ * . Moreover, in the case of over z = 3, coth(z) in Eqs. (2) ~ (7) can be replaced with one and Eq. (8) becomes a BR-BCS T c .
Furthermore, we briefly note the physical meaning of ρ. For instance, it means that, in the case of ρ = 1, the whole measurement region is filled with a correlated metal of one electron per atom in real space, (inset in Fig. 2a), and the band is half-filled in k-space. In the case of ρ = 0.5, 50% of the measurement region is the metal in real space. Moreover, a condition of ρ = 1 is not defined due to the inability of U/U c = 1 at m*/m = 1/(1 − (U/U c ) 2 ) in the BR picture 29 . That is, neither the point of ρ = 1 nor half filling is attainable. This indicates that the correlated material is intrinsically inhomogeneous, which is the characteristic of the correlated material.

Results and discussions
In the superconducting state, the electron-phonon interaction, V e-ph , forming the Cooper pair (pairing in k-space, time-reversed states) in BCS theory is fixed as a constant in real space and k space. This indicates the Cooper pair is a pair in real space (so called bipolaron), such as the pair potential Δ(r) proportional to V e-ph = − V(r 1 ,r 2 )δ(r 1 -r 2 ) suggested in the Bogolubov-de Genes (BdG) theory 28,40,41 . The BdG theory derives the BCS formula for superconductors not only without impurities explained by BCS theory but also with nonmagnetic impurities both making a boundary between metal and nonmetal and not suppressing the superconducting gap 42 ; this is an extension of the BCS theory. For a logical deduction of the constant, we consider an intersite charge-density-wave (CDW) potential as an electron-phonon interaction, V CDW = − (g 2 /2Mω 2 )δq 2 , such as the CDW with a charge disproportionation between nearest neighbor sites, δq ≡ δ(q i -q j ) = 2e, of BaBiO 3 with the set Bi 3+ (6s 2 , the two electrons form bipolaron as a real-space pair) and Bi 5+ (6s 0 ) 43,44 (necessarily see "Methods"); the V CDW has an immobile bipolaron in real-space, thus indicating a set of both a paired occupied state (bipolaron) with two electrons on a site and an unoccupied state without electron at the nearest neighbor site. A range of the intersite CDW potential that reaches out in real space is within two lattice constants of 6~10 Å when the lattice constant in a metal is considered 4 ± 1 Å. Experimental evidence of the CDW in oxide superconductors is a distortion of octahedral structure observed just below T c 45,46 and discontinuity 27 of the bulk modulus at T c . For superconductivity, when the CDW potential is introduced, the on-site critical Coulomb energy U c in the BR picture should be present at the bipolaron, then, as a nonlocal potential, V e-ph = V CDW + U c < 0 is considered a constant, because V CDW and U c are determined as fixed values in a crystal. Since U c is very large and constant, V e-ph becomes extremely small or can approach but not reach zero; this explains why λ BCS = N(0)V e-ph should be small; further, N(0) is also small in an uncorrelated metal 47 (see "Methods"). Then, the bipolaron can tunnel through the CDW potential to the next site; the supercurrent flows, which indicates the bipolaron has changed into the mobile Cooper pair in k-space (so called the mobile bipolaron) due to the U c . Moreover, in the case of a strong coupling with a large V e-ph , the Cooper pair can be trapped. Thus, we assert that U c leads to superconductivity and that, although λ * in Eq. (6) is large (over one) (see Ti-2223 and Hg-1223 in Table 1), T c of Eq. (6) is into weak coupling due to small V e-ph in λ BCS (Table 1).
Subsequently, the coherence length was known as approximately ξ 0 ≈ 5 Å 34 , within the range of two-lattice constant. The radius of the Cooper pair in real space 48 was given as r Cooper pair = πξ 0 . The coherence length, utilizing both the pair potential Δ(r) = Δ(0) at r = 0 calculated from the generalized BdG theory and the effective mass m * , was given as where Δ(0) = 0.2ħω D and ξ 0 = 0.2a for a nano crystal of a size of a = 15 nm was evaluated 49 . Moreover, Deloof et al. 49 stated that the computational effect is reduced by increasing the effective mass and the coupling constant by decreasing the sample size. This author, according to the concept described here, adds that the large effective mass coming from the on-site Coulomb U can reduce the coherence length to a short range of two-lattice constant. A model of superconductivity based on the CDW has been reported 44 .
We apply the T c of Eq. (6) to the experimental data for T c with a transition pressure 8 , using Θ D ≈ 1250 K in a hydride mentioned by Ashcroft 1 . Note that the Θ D is not an accurate value because it is not yet known. The Θ D is used to check whether the T c of Eq. (6) can rise to room temperature or not. The T c values in Eq. (6) seem to rise to room temperature, as shown in Fig. 3. A relation of P vs. ρ is given in the caption of Fig. 3. The obtained parameters are given in Table 1. The obtained λ * s are over 0.435, the weak coupling limit of BCS theory. When precisely calculated Θ D s for the hydrides of H 3 S, D 3 S, LaH 10 , and LaH x are used 50 , the λ * s are also more than 0.435 and less than one (Table 1). We assert that the metallization is accelerated with increasing pressure, which is regarded as the increase in ρ. As evidence of the increased metallization induced by the first-order IMT, a jump in ρ is observed, as shown in Fig. 3. Furthermore, although λ * s are over one for Ti-2223 and Hg-1223 in Table 1 www.nature.com/scientificreports/ the large λ * s are caused by the large effective mass (large density of states) and not a large potential V e-ph , such as the strong coupling potential V Migdal used in the Eliashberg formalism. Moreover, in Table 1, λ * = 0.384 for Pb, known as strong coupling of λ * = 1.12 21 and 1.55 22 , is less than λ * = 0.435 of the weak coupling limit in BCS theory. We briefly discuss a process of the IMT and a change in the correlation strength under high pressure. Compound materials are necessarily inhomogeneous and have an impurity level reflecting the semiconducting behavior. When pressure, temperature, strain, and chemical doping, among other energies are applied to the materials, the Mott-indirect IMT occurs by excitation of the impurity bound charges [37][38][39] . In the underdoped region, as the pressure increases, the extent of the correlated-metal region, ρ, increases due to the indirect IMT (percolation). Therefore, in some materials, at low temperatures, superconductivity appears. Decreasing the temperature reduces the size of the unit volume of the correlated metal (i.e., contraction of the unit volume), which causes an increase in the correlation strength. Additionally, applying pressure to the correlated materials leads to metallization as well as contraction of the unit volume, resulting in both an enhanced correlation and an increase of ρ. Thus, the density of states as a function of the effective mass diverges near ρ = 1 due to strong correlation of a constant value of κ BR ≡ U/U c ≈ 1 (not one), as shown in Fig. 2a. Thus, the T c in Eq. (6) rapidly increases, which is the T c divergence, as shown in Fig. 2b.  www.nature.com/scientificreports/ Furthermore, in the BCS-based mechanism for all kinds of superconductors, when the correlation effect in the density of states is introduced, the coupling constant, λ BCS , should be replaced with λ * = Aλ BCS including the correlation effect. When λ BCS < 0.1 with a small value 47 (see "Methods"), instead of λ * , is applied to Eq. (5), T c is not obtained; this is a weak point of BCS theory. This finding indicates that superconductivity does not occur without correlation; this is a mathematical discovery. Until now, to explain low-temperature superconductivity, a value near λ BCS = 0.20 ~ 0.30 has been used, which should really be regarded as λ * . Moreover, the element superconductors explained by BCS theory should be regarded as correlated metals which are different from pure metals such as Au, Ag, or Cu that do not show superconductivity. The metallization in the element superconductors, including a non-metallic phase of few concentrations considered as impurity, is induced by the impurity-driven indirect IMT. This phenomenon is understood by observing the rise in T c when pressure is applied to the element superconductors 51,52 , because the pressure effect does not appear in the pure metal crystals. Additionally, Eq. (6) can describe the high T c of the cuprate superconductors. The λ * values obtained for important cuprate superconductors are given in Table 1. The energy gaps are slightly less than those we observed in the present analysis, which may be attributed to a smaller Θ D . We suspect that the observed Θ D was averaged to the multi-layered and inhomogeneous cuprate system, not measured on only the CuO 2 -layered plane. Accordingly, we assert that the superconductivity for all kinds of superconductors is caused by a change in the electron correlation that occurs due to the volume contraction induced by strong pressure or low temperature; this indicates that U in the correlated metal of the normal state can change to U c of the condensed superconducting gapped state, which leads to the electron-phonon interaction at T c .

Conclusion
The T c,BR-BCS with the electron correlation of Eq. (6) accounts for the high T c . It can be applied to all kinds of superconductors, such as element superconductors, compound superconductors, cuprate superconductors, and hydride superconductors, among others. The diverging T c measured in the hydrides 8 is responsible for the pressure-driven first-order IMT. Superconductivity can be attributed to the transition of the Bose-Einstein condensation from U to U c , which derives from the volume contraction by applied pressure or low temperature.

Methods
Evaluation of the strong-coupled-McMillan T c . μ* ≡ μ/(1 + μln(E F /ћω)) should be satisfied with μ* << 1 21,24 . μ* = (1 − 2α) 0.5 /ln(Θ D /1.45T c ) at λ < < 1 was obtained from neglecting 'strong-coupling' correction term 21 Fig. 1a are drawn together. The T c calculations cannot be correct, because the Debye temperature, Θ D , is not correct; here Θ D = 1250 K was predicted in a hydride 1 , which indicates that Eq. (6) approaches the room-temperature T c . The jump in ρ is observed as evidence of the first-order IMT. The detailed information is provided in Table 1. At line 1 over P transition ≈ 220 GPa, the relation between ρ and pressure P is P = 11,759.62ρ − 11,359.59, where the slope has a standard error of 747.35 and the standard error of the intercept is 737.64. At line 2 below P transition , the relation between ρ and pressure is given as P = 25,230.15ρ − 24,644.25, where the slope has a standard error of 4660.97 and the standard error of the intercept is 4588.50. The slope of line 1 is much larger than that of line 2, revealing the diverging behavior. Derivation of the charge density-wave potential, V CDW . For metal, we consider the breathing mode (harmonic oscillation) of an atom, then E Breath = 1 2 kx 2 , where k = Mω 2 , x is a small deviation from atomic position induced by the oscillation, M is a mass of the atom, and ω is atom ′ s oscillation frequency . Next, for insulator, we consider the breathing mode distortion, E Breath−distortion = gδqx , where g is a proportional parameter, δq = q i − q j is a charge disproportionation between nearest neighbor sites. The total Energy, E CDW = E Breath + E Breath−distortion = 1 2 kx 2 + gδqx, is given. At a condition, dE CDW dx = 0, x 0 = − gδq k is obtained. When x is replaced with x 0 in E CDW , E CDW = − g 2 (δq) 2 2k = − g 2 (δq) 2 2Mω 2 , is obtained. On average of E CDW , < E CDW >= − <g 2 >(δq) 2 2M<ω 2 > , is given. When δq = 0, the electronic structure is one electron per atom of metal. In δq = 2e case, two electrons are occupied in a site and the nearest neighbor site is empty; this is the bipolaronic system. When δq = 1e, < E CDW >= − <g 2 > 2M<ω 2 > , is similar to λ/N(0) = 2 M<ω 2 > , in Eq. (23) (this is also CDW potential) in Ref. 21 (MacMillan's paper). When spin is considered, 2 < E CDW >= N(0) is same. On the basis of this CDW logic, Eq. (23) in Ref. 21 has an electronic structure in which one electron is occupied in a site and the nearest neighbor site is empty. Then, the number of electrons is half of total electrons in the system, which has a disagreement not satisfied with the metal condition (one electron per atom, that is, half filling) in the normal state (?); this is not bipolaron but just polaron. Finally, we assert that the electron-phonon interaction indicates the CDW interaction. www.nature.com/scientificreports/ Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http:// creat iveco mmons. org/ licen ses/ by/4. 0/.